Black ink composition, ink set, and image forming method

ABSTRACT

A black ink composition includes: carbon black and a water-insoluble resin that covers at least a part of the surface of the carbon black; a cyan pigment and a water-insoluble resin that covers at least a part of the surface of the cyan pigment; a magenta pigment and a water-insoluble resin that covers at least a part of the surface of the magenta pigment; water-insoluble resin particle; and water, wherein a content ratio of the carbon black is from 1.0 to 2.0% by mass with respect to the total mass of the composition, and a total amount of pigments is from 1.8 to 3.5% by mass with respect to the total mass of the composition. The black ink composition can be used in an ink set and an image forming method.

CROSS-REFERENCE TO RELATED APPLICATION

This application is based on and claims priority under 35 USC 119 fromJapanese patent Application No. 2010-217823 filed on Sep. 28, 2010, thedisclosure of which is incorporated by reference herein.

BACKGROUND OF THE INVENTION

1. Technical Field

The present invention relates to a black ink composition containingcarbon black, an ink set including the composition, and an image formingmethod.

2. Description of the Related Art

Inkjet recording methods allow recording of high-quality images onvarious recording media by ejecting droplets of inks from a number ofnozzles provided at an inkjet head. Therefore, inkjet recording methodsare widely used.

Pigments are widely used as a coloring agent, which is a component of anink. In inks, pigments are used in a state of being dispersed in amedium such as water. When pigments are used in the dispersed state,important factors include the diameter of the dispersed particles,stability after dispersing, size uniformity, ejectability from ejectionnozzles, and image density. Various studies are carried out ontechniques for improving such factors.

Further, in some cases, recording on plain sheet provides onlyinsufficient quality in terms of rubbing resistance of the formed image(fixability), resolution, and the like, as well as image density. Thereis a tendency for the insufficiency in quality to become moreconspicuous when the inkjet recording speed is increased. Specifically,compatibility with high-speed recording in a single-pass manner ratherthan a shuttle-scan manner is requested in terms of the rubbingresistance and resolution of the formed image. In the single-passrecording, recording can be carried out by a single head operation.

Meanwhile, in addition to the image density, generation of unevenness inimage has to be considered from the viewpoint of image quality becauseunevenness in image, such as streak-shaped unevenness, may be generatedwhen an image is recorded on plain paper or the like. The generation ofunevenness is significant when high-speed inkjet recording is carriedout. Specifically, streak-shaped unevenness is more likely to begenerated in an image when the image is recorded at high speeds in asingle-pass manner, which enables recording with one operation of ahead, as compared to a shuttle-scan manner. The unevenness isparticularly remarkable when an image of an intermediate tone of black(i.e., gray tone) is formed.

When high-speed recording is carried out in a single-pass manner, aninkjet head having a width that is equal to the width of a recordingmedium is used. However, in such a case, unevenness in hue tends to begenerated in the width direction owing to a variation in ejectionamounts of ink along the width direction. The unevenness in hue isparticularly significant when an image of intermediate tone of black(i.e., gray tone), which is achromatic, is formed.

Among pigments used in inks for inkjet recording, carbon black is widelyused as a black pigment. A technique in which a pigment other thancarbon black, such as a cyan pigment, is used together with carbon black(hereinafter abbreviated to CB) is also known.

Specifically, a pigment dispersion aqueous recording liquid is disclosedin, for example, Japanese Patent Application Laid-Open (JP-A) No.2004-285344. This pigment dispersion aqueous recording liquid containscarbon black (CB) and a pigment other than CB, such as a cyan pigment,together with a urethane resin. Further, an aqueous ink for inkjetrecording that contains polymer particles containing carbon black isdisclosed in, for example, JP-A No. 2009-144007.

Regarding an ink containing carbon black (CB), a neutral black ink orblack ink set which contains carbon black as well as a cyan pigment anda magenta pigment is disclosed (see, for example, Japanese PatentApplication Laid-Open (JP-A) No. 2005-213505, or JP-A No. 2003-55592),which enables improvements in tone of an yellowish or brownish image,and provides excellent color reproducibility.

Furthermore, a black ink is disclosed (see, for example, JP-A No.2009-132766), which contains a dispersion of surface-treated blackpigments capable of being dispersed in water even in the absence of adispersant, a magenta pigment-containing polymer particle dispersion, acyan pigment-containing polymer particle dispersion, a yellowpigment-containing polymer particle dispersion, and resin emulsion. Itis disclosed that the black ink is excellent in glossiness of image,ejection property, and the like.

On the other hand, a pigment, being hard powder, has a problem in thatthe pigment may easily damage a nozzle surface when an ink is wiped offfor maintenance of a nozzle for ejecting the ink. In particular, whencarbon black, from among various pigments, is contained in an ink, theink tends to damage a nozzle surface as compared with a case in which acolor ink containing an organic pigment is used.

SUMMARY OF THE INVENTION

Techniques of using carbon black in combination with a pigment otherthan a black pigment, such as a cyan pigment or magenta pigment, havebeen proposed, such as the techniques described in the pieces of relatedart described above. However, when carbon black is simply mixed with apigment of another color, it is only expected that color reproducibilityis improved to a certain degree, and it is difficult to preventstreak-shaped unevenness, unevenness in hue, and the like, which aregenerated in high-speed recording in single-pass manner.

Use of an ink containing carbon black tends to exacerbate nozzle damage,as compared to cases in which inks containing other organic pigments areused. The nozzle damage may be suppressed by decreasing the contentratio of carbon black. However, a simple reduction in the content ratioof carbon black may make it impossible to obtain a desired blackdensity, may shift the color obtained when, for example, a gray tone isdesired, and may provide only a yellowish hue.

When the amounts of ink components, such as polymer particles, otherthan pigment are increased, the proportion of carbon black in an imageis relatively decreased, as a result of which the shielding ratio isdecreased, and a change in hue such as yellow tinge tends to occur.Accordingly, it has not been possible to obtain a desired black color oran intermediate tone, such as gray, with less yellow tinge, whilealleviating streak-shaped unevenness in an image and improvingmaintenance properties.

The present invention has been made in view of the above, and provides ablack ink composition and an ink set, each of which enables provision ofan image having black color with less yellow tinge or an intermediatetone (for example, gray) with less yellow tinge, and suppressesstreak-shaped unevenness in an image, unevenness in hue in an image, andgeneration of nozzle damage during maintenance. The present inventionfurther provides an image forming method by which generation ofstreak-shaped unevenness and generation of unevenness in hue areprevented, and an image of black color or an intermediate tone (forexample, gray) with less yellow tinge can be obtained, while controllingdamage to a nozzle surface at a low level.

Aspects of the invention include the following.

<1> A black ink composition, comprising:

carbon black and a first water-insoluble resin that covers at least apart of a surface of the carbon black;

a cyan pigment and a second water-insoluble resin that covers at least apart of a surface the cyan pigment;

a magenta pigment and a third water-insoluble resin that covers at leasta part of a surface of the magenta pigment;

water-insoluble resin particles; and

water,

wherein a content ratio of the carbon black is from 1.0 to 2.0% by masswith respect to a total mass of the composition, and a total amount ofpigments is from 1.8 to 3.5% by mass with respect to the total mass ofthe composition.

<2> The black ink composition according to <1>, wherein a content of thewater-insoluble resin particles is larger than a total amount ofpigments, at least a part of surfaces of which are coated withwater-insoluble resins, and the water-insoluble resins that cover the atleast a part of surfaces of the pigments.

<3> The black ink composition according to <2>, wherein a ratio of thecontent of the water-insoluble resin particles to the total amount ofpigments, at least a part of surfaces of which are coated withwater-insoluble resins, and the water-insoluble resins that cover the atleast a part of surfaces of the pigments, is more than 1.0 but not morethan 4.0.

<4> The black ink composition according to <1>, wherein thewater-insoluble resin particles comprise self-dispersing polymerparticles.

<5> The black ink composition according to <1>, wherein thewater-insoluble resin particles have a Tg of 100° C. or higher.

<6> The black ink composition according to <1>, further comprising asolid humectant.

<7> The black ink composition according to <6>, wherein the humectant isselected from urea, a urea derivative, or a mixture thereof.

<8> The black ink composition according to <1>, further comprising ayellow pigment and a fourth water-insoluble resin that covers at least apart of a surface of the yellow pigment.

<9> An ink set, comprising:

the black ink composition according to <1>; and

a treatment liquid comprising an aggregation component which is capableof causing formation of an aggregate when contacting the black inkcomposition.

<10> An image forming method, comprising:

applying the black ink composition according to <1> to a recordingmedium by an inkjet method; and

applying a treatment liquid to the recording medium, the treatmentliquid comprising an aggregation component which is capable of causingformation of an aggregate when contacting the black ink composition.

<11> The image forming method according to <10>, wherein the applying ofthe black ink composition comprises applying the black ink compositionby a piezoelectric inkjet method.

<12> The image forming method according to <11>, further comprisingheating an image formed through the applying of the black inkcomposition and the applying of the treatment liquid, to fix the imageon the recording medium.

According to the invention, a black ink composition and ink set areprovided, each of which enables provision of an image having black colorwith less yellow tinge or an intermediate tone (for example, gray) withless yellow tinge, and suppresses streak-shaped unevenness in an image,unevenness in hue in an image, and generation of nozzle damage duringmaintenance.

Furthermore, according to the invention, an image forming method isprovided by which generation of streak-shaped unevenness and generationof unevenness in hue are prevented, and an image of black color or anintermediate tone (for example, gray) with less yellow tinge can beobtained, while controlling damage to a nozzle surface at a low level.

DETAILED DESCRIPTION OF THE INVENTION

Hereinbelow, a black ink composition of the invention, and an ink setincluding the black composition and an image forming method in which theblack ink composition is used are described in detail.

As used herein, the scope of “maintenance” includes maintaining arecording head that ejects an inkjet recording ink composition and theejection performance thereof in an initial state or in a state close tothe initial state, and further encompasses having the recording headserviced and maintained in a better state by cleaning the recordinghead.

<Black Ink Composition>

A black ink composition of the invention (which may be referred to as“ink composition” hereinbelow) is an aqueous composition including atleast:

carbon black and a first water-insoluble resin that covers at least apart of the surface of the carbon black;

a cyan pigment and a second water-insoluble resin that covers at least apart of the surface of the cyan pigment;

a magenta pigment and a third water-insoluble resin that covers at leasta part of the surface of the magenta pigment;

water-insoluble resin particles; and

water,

and in which the content ratio of the carbon black (excluding the firstwater-insoluble resin, the same applies hereinafter) is from 1.0% bymass to 2.0% by mass with respect to the total amount of thecomposition, and the total amount of pigments (excluding coating resinssuch as the water-insoluble resins, the same applies hereinafter) isfrom 1.8% by mass to 3.5% by mass with respect to the total amount ofthe composition.

The black ink composition of the invention may further include othercomponents such as an organic solvent or a surfactant, if necessary.

In the invention, the black ink composition, which includes carbon black(which may be abbreviated to “CB”) as a black colorant for forming ablack ink, has a configuration in which:

the ink composition includes a cyan pigment and a magenta pigmenttogether with the CB;

at least a part of the surfaces of the particles of each of the CB, cyanpigment, and magenta pigment is coated with a water-insoluble resin;

the content ratio of the carbon black, which has high tendency to damagethe surface of a head nozzle, is decreased, and resin particles, whichhave low tendency to damage the surface of a head nozzle, are included;and

the amounts of pigments (excluding coating resins such aswater-insoluble resins) are adjusted such that the total mass ofpigments is at a certain ratio relative to the total amount of the ink.

Due to this configuration, generation of damage to the head nozzlesurface during maintenance is regulated to be low, and when, forexample, a black image or an image of an intermediate tone such as grayis formed at a high speed in a single-pass manner, generation ofstreak-shaped unevenness or hue unevenness in an image is prevented, andan achromatic image in which a change in color from a black orintermediate tone image is suppressed can be obtained.

When, as described above, the amount of carbon black (CB) contained inthe ink composition is decreased in order to prevent generation ofstreak-shaped unevenness and damage to the surface of a head nozzle, butis still capable of maintaining a black density and the colorreproducibility of an achromatic color, and the ink composition furtherincludes a resin-coated cyan pigment and a resin-coated magenta pigmentin amounts such that the total pigment amount falls within a certainrange, a color change (yellowing) caused by the decrease in the CBamount and generation of striped-shape unevenness in an image areprevented, and damage to the surface of a head nozzle, which tends tooccur when the head nozzle is wiped during maintenance, is prevented.The hue unevenness caused during printing in a single-pass manner iscaused by slight fluctuation in ejection from an inkjet head, and may beprevented by adjusting the CB amount and the total amount of pigments tobe within the respective specific ranges such that a change in theejection amount (i.e., image dot ratio) does not lead to a change inhue. Furthermore, generation of damage on a nozzle surface is furthersuppressed by coating the CB, the cyan pigment, and the magenta pigmentwith at least one water-insoluble resin and including water-insolubleresin particles, in addition to reducing the amount of CB.

(Resin-Coated Carbon Black)

The black ink composition of the invention includes at least one carbonblack at least a part of the surface of which is coated with awater-insoluble resin (which may be referred to as “resin-coated CB” or“resin-coated carbon black” hereinbelow). The resin-coated CB is aparticle obtained by coating a part or all of the particle surface ofcarbon black (CB) with a water-insoluble resin, and is included in adispersed state in the ink composition.

—Carbon Black—

Examples of carbon blacks include a carbon black produced by a knownmethod such as a contact method, a furnace method, or a thermal method.Specific examples thereof include furnace black, thermal lamp black,acetylene black, and channel black.

Specific examples of carbon blacks include, but are not limited to,RAVEN 7000, RAVEN 5750, RAVEN 5250, RAVEN 5000 ULTRA II, RAVEN 3500,RAVEN 2000, RAVEN 1500, RAVEN 1250, RAVEN 1200, RAVEN 1190 ULTRA II,RAVEN 1170, RAVEN 1255, RAVEN 1080, RAVEN 1060, RAVEN 700 (all of whichare trade names, manufactured by Columbian Chemicals Company), REGAL1400R, REGAL 1330R, REGAL 1660R, MOGUL L, BLACK PEARLS L, MONARCH 700,MONARCH 800, MONARCH 880, MONARCH 900, MONARCH 1000, MONARCH 1100,MONARCH 1300, MONARCH 1400 (all of which are trade names, manufacturedby Cabot Corporation), COLOR BLACK FW1, COLOR BLACK FW2, COLOR BLACKFW2V, COLOR BLACK 18, COLOR BLACK FW200, COLOR BLACK S 150, COLOR BLACKS 160, COLOR BLACK S170, PRINTEX 35, PRINTEX U, PRINTEX V, PRINTEX 140U,PRINTEX 140V, SPECIAL BLACK 6, SPECIAL BLACK 5, SPECIAL BLACK 4A,SPECIAL BLACK 4 (all of which are trade names, manufactured byEvonik-Degussa GmbH), and No. 25, No. 33, No. 40, No. 45, No. 47, No.52, No. 900, No. 2200B, No. 2300, MCF-88, MA600, MA7, MA8, MA100 (all ofwhich are trade names, manufactured by Mitsubishi Chemical Corporation).

—Water-Insoluble Resin—

Examples of the water-insoluble resin with which the carbon black (CB)is coated include [1] a polymer including a repeating unit (a)represented by the following Formula (1) and a repeating unit (b) havingan ionic group, and [2] a polymer including a structural unit derivedfrom a salt-forming-group-containing monomer (c) and at least onestructural unit derived from a styrenic macromonomer (d) and/or ahydrophobic monomer (e).

As used herein, “insoluble” means that, when a polymer is mixed with anaqueous medium at 25° C., the amount of polymer that dissolves in theaqueous medium is 10% by mass or less with respect to the total amountof polymer mixed with the aqueous medium.

[1] Polymer containing repeating unit (a) represented by Formula (1) andrepeating unit (b) having ionic group

The polymer contains at least one repeating unit represented by Formula(1) and at least one repeating unit having an ionic group, and mayfurther contain, if necessary, another structural unit such as ahydrophobic repeating unit other than the repeating unit represented byFormula (1) or a hydrophilic repeating unit having a non-ionicfunctional group.

<Repeating Unit (a) Represented by Formula (1)>

In Formula (1), R₁ represents a hydrogen atom, a methyl group, or ahalogen atom; L₁ represents *—COO—, *—OCO—, *—CONR₂—, *—O—, or asubstituted or unsubstituted phenylene group, R₂ represents a hydrogenatom or an alkyl group having from 1 to 10 carbon atoms, and “*” shownin the group represented by L₁ indicates a position at which L₁ isconnected to the main chain; L₂ represents a single bond or a divalentlinking group; and Ar represents a monovalent aromatic ring groupderived from an aromatic ring.

In Formula (1), R₁ represents a hydrogen atom, a methyl group, or ahalogen atom, and preferably represents a methyl group.

L₁ represents *—COO—, *—COO—, *—CONR₂—, *—O—, or a substituted orunsubstituted phenylene group. When L₁ represents a phenylene group, thephenylene group is preferably an unsubstituted phenylene group. R₂represents a hydrogen atom or an alkyl group having from 1 to 10 carbonatoms.

L₂ represents a single bond or a divalent linking group. The divalentlinking group is preferably a linking group having from 1 to 30 carbonatoms, more preferably a linking group having from 1 to 25 carbon atoms,even more preferably a linking group having from 1 to 20 carbon atoms,and particularly preferably a linking group having from 1 to 15 carbonatoms.

In particular, examples of most preferable linking groups include analkyleneoxy group having from 1 to 25 carbon atoms (more preferably,having from 1 to 10 carbon atoms), an imino group (—NH—), a sulfamoylgroup, a divalent linking group containing an alkylene group, such as analkylene group having from 1 to 20 carbon atoms (more preferably, havingfrom 1 to 15 carbon atoms) or an ethylene oxide group [—(CH₂CH₂O)_(n)—,n=1 to 6], and a group obtained by combining two or more types oflinking group selected from the above.

Ar represents a monovalent group derived from an aromatic ring.

The aromatic ring of the monovalent group represented by Ar is notparticularly limited, and examples thereof include a benzene ring, acondensed aromatic ring having 8 or more carbon atoms, an aromatic ringhaving a hetero ring condensed thereto, and an aromatic ring obtained bycondensing at least two benzene rings.

The term “condensed aromatic ring having 8 or more carbon atoms”described above refers to an aromatic ring which has 8 or more carbonatoms, and of which rings are composed of two or more benzene ringscondensed with each other, or of at least one type of aromatic ring andat least one alicyclic hydrocarbon condensed with the at least one typeof aromatic ring. Specific examples thereof include naphthalene,anthracene, fluorene, phenathrene, and acenaphthene.

The term “aromatic ring condensed with a heterocycle” described aboverefers to a compound that includes at least one aromatic compound freeof a heteroatom (preferably, a benzene ring) and at least oneheteroatom-containing cyclic compound condensed with the at least onearomatic compound. Here, the heteroatom-containing cyclic compound ispreferably a 5-membered ring or a 6-membered ring. The heteroatom ispreferably a nitrogen atom, an oxygen atom, or a sulfur atom. Theheteroatom-containing cyclic compound may have plural heteroatoms. Inthis case, the heteroatoms may be the same as or different from eachother.

Specific examples of hetero ring having an aromatic ring condensedthereto include phthalimide, acridone, carbazole, benzoxazole, andbenzothiazole.

Specific examples of a monomer for forming a repeating unit representedby Formula (1) may include vinyl monomers such as (meth)acrylates,(meth)acrylamides, styrenes, and vinyl esters.

In the present invention, a hydrophobic structural unit having anaromatic ring bonded to an atom in the main chain via a linking grouphas a structure in which an aromatic ring is bonded to an atom in themain chain of the water-insoluble resin via a linking group, and doesnot directly binds to an atom in the main chain of the water-insolubleresin. Therefore, a suitable distance is maintained between thehydrophobic aromatic ring and a hydrophilic structural unit, and thus,an interaction between the water-insoluble resin and the pigment isenhanced, resulting in strong adsorption and further improvement of thedispersibility.

Specific examples of a monomer for forming a repeating unit representedby Formula (1) include, but are not limited to, the following monomers.

Ar in the repeating unit (a) represented by Formula (1) is preferably amonovalent group derived from benzyl (meth)acrylate, phenoxyethylacrylate, phenoxyethyl methacrylate, acridone, or phthalimide, from theviewpoint of the dispersion stability of the coated pigment.

The repeating units may be used singly, or in combination of two or morethereof.

The content ratio of the repeating unit represented by Formula (1) in apolymer is preferably from 5 to 25% by mass, and more preferably from 10to 18% by mass, with respect to the total mass of the polymer. When thecontent ratio is 5% by mass or higher, generation of image defects suchas white spots may be significantly prevented. When the content ratio is25% by mass or less, problems in production suitability which may becaused by decrease in solubility of the polymer in a polymerizationreaction solution (e.g., methyl ethyl ketone) hardly arise.

<Other Hydrophobic Repeating Unit>

The polymer [1] preferably further contains, as a hydrophobic structuralunit, a hydrophobic repeating unit other than the repeating unitrepresented by Formula (1). Examples of a hydrophobic repeating unitother than the repeating unit represented by Formula (1) include astructural unit derived from a vinyl monomer such as a(meth)acrylate-containing compound, a (meth)acrylamide-containingcompound, a styrenic compound, or a vinyl ester, each of which is not ahydrophilic structural unit (for example, each of which has nohydrophilic functional group); and a hydrophobic structural unit havingan aromatic ring which is bonded to an atom of the main chain thereofvia a linking group. The structural units may be used alone, or incombination of two or more thereof. As a result of the incorporation ofa repeating unit having properties that are intermediate between theproperties of a repeating unit represented by Formula (1) and theproperties of the hydrophilic repeating unit described below, thedispersion properties and the dispersion stability of the resultantpigment dispersion can further be improved.

Examples of the (meth)acrylate-containing compound include alkyl(meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate,butyl (meth)acrylate, isobutyl (meth)acrylate, and hexyl (meth)acrylate.In particular, an alkyl (meth)acrylate having an alkyl moiety havingfrom 1 to 5 carbon atoms is preferable. Specifically, examples ofpreferable (meth)acrylates include methyl (meth)acrylate, ethyl(meth)acrylate, and butyl (meth)acrylate, and methyl (meth)acrylate andethyl (meth)acrylate are particularly preferable.

Examples of the (meth)acrylamide-containing compound includeN-cyclohexyl (meth)acrylamide, N-(2-methoxyethyl) (meth)acrylamide,N,N-diallyl (meth)acrylamide, and N-allyl (meth)acrylamide.

Examples of the styrenic compound include styrene, methylstyrene,dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene,n-butylstyrene, tert-butylstyrene, methoxystyrene, butoxystyrene,acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene,chloromethyl styrene, hydroxystyrene protected with a group (e.g.,t-Boc) capable of deprotection using an acidic substance,hydrosystyrene, methyl vinylbenzoate, α-methylstyrene, andvinylnaphthalene. Among these, styrene and α-methylstyrene arepreferable.

Examples of vinyl esters include vinyl acetate, vinyl chloroacetate,vinyl propionate, vinyl butyrate, vinyl methoxyacetate, and vinylbenzoate. Among these, vinyl acetate is preferable.

<Repeating Unit (b) Having Ionic Group>

Examples of repeating units having an ionic group include a repeatingunit derived from a monomer having an ionic group such as a carboxylgroup, a sulfo group, or a phsphonate group. More specifically, themonomer having an ionic group may be a vinyl monomer having an ionicfunctional group, such as (meth)acrylic acid, a(meth)acrylate-containing compound, a (meth)acrylamide-containingcompound, or a vinyl ester. The repeating unit having an ionic group canbe introduced into the polymer by, for example, polymerization of acorresponding monomer or introduction of an ionic group into the polymerchain after polymerization.

From among the above repeating units having an ionic group, a repeatingunit derived from acrylic acid or a repeating unit derived frommethacrylic acid is preferable. Polymer [1] preferably includes astructural unit derived from acrylic acid or a structural unit derivedfrom methacrylic acid or both.

It is preferable that the content of the repeating unit (b) having anionic group in polymer [1] is 15% by mass or lower with respect to theentire mass of the polymer, and that the repeating units having an ionicgroup in polymer [1] include a structural unit (repeating unit) derivedfrom (meth)acrylic acid.

When the content of the repeating unit (b) having an ionic group is 15%by mass or lower with respect to the entire mass of the polymer,excellent dispersion stability can be realized. In particular, the ratioof repeating units (b) having an ionic group is more preferably from 5%by mass to 15% by mass, and still more preferably from 7% by mass to 13%by mass, relative to the entire mass of the polymer, from the viewpointof dispersion stability.

The polymer [1] is capable of being stably present in an aqueous inkcomposition, and mitigates adhesion and deposition of aggregates onto aninkjet head or the like, and has excellent properties with respect tothe removability of adhered aggregates. From these viewpoints, thepolymer [1] may further contain a hydrophobic structural unit other thanthe repeating unit represented by Formula (1) and/or a hydrophilicstructural unit other than the repeating unit (b) having an ionic group.

<Hydrophilic Structural Unit>

The hydrophilic structural unit other than the repeating unit (b) havingan ionic group may be, for example, a repeating unit derived from amonomer having a nonionic hydrophilic group, examples of which include avinyl monomer having a nonionic hydrophilic group such as a(meth)acrylate-containing compound having a nonionic hydrophilicfunctional group, a (meth)acrylamide-containing compound having anonionic hydrophilic functional group, or a vinyl ester having anonionic hydrophilic functional group.

Examples of the nonionic hydrophilic functional group include a hydroxylgroup, an amino group, an amido group of which the nitrogen atom isunsubstituted, and an alkylene oxide such as polyethylene oxide orpolypropylene oxide, which are described below.

The monomer for forming a hydrophilic repeating unit having a nonionichydrophilic group is not particularly limited, as long as the monomerhas a functional group capable of forming a polymer, such as anethylenic unsaturated double bond, and a nonionic hydrophilic functionalgroup. The monomer for forming a hydrophilic repeating unit having anonionic hydrophilic group may be selected from known monomers.Preferable examples thereof include hydroxyethyl (meth)acrylate,hydroxybutyl (meth)acrylate, (meth)acrylamide, aminoethyl acrylate,aminopropyl acrylate, and a (meth)acrylate that contains an alkyleneoxide polymer.

The hydrophilic repeating unit having a nonionic hydrophilic group canbe formed by, for example, polymerization of a corresponding monomer orintroduction of a nonionic hydrophilic functional group into the polymerchain after polymerization.

The hydrophilic repeating unit having a nonionic hydrophilic group ismore preferably a hydrophilic structural unit having an alkylene oxidestructure. The alkylene portion of the alkylene oxide structure ispreferably an alkylene having from 1 to 6 carbon atoms, more preferablyan alkylene having from 2 to 6 carbon atoms, and particularly preferablyan alkylene having from 2 to 4 carbon atoms, from the viewpoint ofhydrophilicity. The polymerization degree of the alkylene oxidestructure is preferably from 1 to 120, more preferably from 1 to 60, andparticularly preferably from 1 to 30.

It is also preferable that the hydrophilic repeating unit having anonionic hydrophilic group is a hydrophilic repeating unit containing ahydroxyl group. The number of hydroxyl groups in the repeating unit isnot particularly limited, and is preferably from 1 to 4, more preferablyfrom 1 to 3, and particularly preferably from 1 to 2, from theviewpoints of the hydrophilicity of the water-insoluble resin and thecompatibility with solvent or other monomers at the time ofpolymerization.

A suitable ratio between hydrophilic repeating units and hydrophobicrepeating units (including a repeated structure represented by the aboveFormula (1)) in polymer [1] depends on the strength of thehydrophilicity/hydrophobicity of the individual repeating units. Inpolymer [1], the ratio of hydrophilic repeating units is preferably 15%by mass or lower relative to the entire mass of the water-insolubleresin (polymer [1]). Here, the ratio of hydrophobic repeating units ispreferably higher than 80% by mass relative to the entire mass of thewater-insoluble resin, and more preferably 85% by mass or higherrelative to the entire mass of the water-insoluble resin.

When the content of hydrophilic repeating units is 15% by mass or less,the amount of components that singly dissolves in an aqueous medium issuppressed, various performances such as dispersing of pigment isexcellent, and favorable ink ejection properties are achieved at thetime of inkjet recording.

The content ratio of hydrophilic repeating units is preferably from morethan 0% by mass to 15% by mass, more preferably from 2 to 15% by mass,still more preferably from 5 to 15% by mass, and particularly preferablyfrom 8 to 12% by mass, relative to the entire mass of thewater-insoluble resin.

The content of aromatic rings in the water-insoluble resin is preferably27% by mass or lower, more preferably 25% by mass or lower, and stillmore preferably 20% by mass or lower, with respect to the entire mass ofthe water-insoluble resin. In particular, the content of aromatic ringsin the water-insoluble resin is further preferably from 15 to 20% bymass, and still further preferably from 17 to 20% by mass, with respectto the entire mass of the water-insoluble resin. A content ratio ofaromatic rings within the above range provides improved resistanceagainst rubbing.

Specific examples of polymer [1] include, but are not limited to, thosedescribed below. Here, “Mw” represents weight average molecular weight.

Phenoxyethyl acrylate/methyl methacrylate/acrylic acid copolymer(50/45/5 [mass %])

Phenoxyethyl acrylate/benzyl methacrylate/isobutylmethacrylate/methacrylic acid copolymer (30/35/29/6 [mass %])

Phenoxyethyl methacrylate/isobutyl methacrylate/methacrylic acidcopolymer (50/44/6 [mass %])

Phenoxyethyl acrylate/methyl methacrylate/ethyl acrylate/acrylic acidcopolymer (30/55/10/5 [mass %])

Benzyl methacrylate/methyl methacrylate/methacrylic acid copolymer(60/30/10 [mass %])

(M-25/M-27) mixture/ethyl methacrylate/methacrylic acid copolymer(15/75/10 [molar ratio], Mw: 49,400, acid value: 65.2 mgKOH/g)

(M-25)/ethyl methacrylate/methacrylic acid copolymer (18/69/13 [molarratio], Mw: 41,600, acid value: 84.7 mgKOH/g)

(M-28/M-29) mixture/ethyl methacrylate/methacrylic acid copolymer(15/85/10 [molar ratio], Mw: 38,600, acid value: 65.2 mgKOH/g)

(M-28)/ethyl methacrylate/methacrylic acid copolymer (20/73/7 [molarratio], Mw: 45,300, acid value: 45.6 mgKOH/g)

[2] Polymer containing structural unit derived from salt-forminggroup-containing monomer (c), structural unit derived from styrenemacromer (d), and/or structural unit derived from hydrophobic monomer(e)

Polymer [2] is a water-insoluble polymer that is preferable from theviewpoint of imparting ejection stability and cleanability. Polymer [2]is more preferably a water-insoluble graft polymer containing astructural unit derived from the styrenic macromer (d). It is preferablethat the water-insoluble graft polymer has, at a main chain thereof, apolymer including a structural unit derived from thesalt-forming-group-containing monomer (c) and a structural unit derivedfrom the hydrophobic monomer (e), and has, at a side chain thereof, astructural unit derived from the styrenic macromer (d). Thewater-insoluble polymer is preferably a water-insoluble vinyl polymerobtained by copolymerization of a monomer mixture including thesalt-forming-group-containing monomer (c) (hereinafter sometimesreferred to as “(c) component”), the styrenic macromer (d) (hereinaftersometimes referred to as “(d) component”), and/or the hydrophobicmonomer (e) (hereinafter sometimes referred to as “(e) component”). Thismonomer mixture is hereinafter sometimes referred to as “monomermixture”.

(Salt-Forming-Group-Containing Monomer(c))

The salt-forming-group-containing monomer (c) is used with a view to,for example, increasing the dispersion stability of the dispersionobtained. Examples of the salt-forming group include a carboxyl group, asulfonic acid group, a phosphoric acid group, an amino group, and anammonium group. Examples of the (c) component include cationic monomersand anionic monomers, specific examples of which include those describedin column 7, line 24 to column 8, line 29 on page 5 of JP-A No.9-286939.

Representative examples of the cationic monomers include unsaturatedamino group-containing monomers and unsaturated ammonium salt-containingmonomers. From among these monomers, N,N-dimethylaminoethyl(meth)acrylate or N—(N′,N′-dimethylaminopropyl)(meth)acrylamide ispreferable.

Representative examples of the anionic monomers include unsaturatedcarboxylic acid monomers, unsaturated sulfonic acid monomers, andunsaturated phosphoric acid monomers.

Examples of unsaturated carboxylic acid monomers include acrylic acid,methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaricacid, citraconic acid, and 2-methacryloyloxymethyl succinic acid.

Examples of unsaturated sulfonic acid monomers include styrenesulfonicacid, 2-acrylamide-2-methylpropanesulfonic acid, 3-sulfopropyl(meth)acrylate, and bis-(3-sulfopropyl)-itaconate.

Examples of unsaturated phosphoric acid monomers include vinylphosphonic acid, vinyl phosphate, bis(methacryloxyethyl)phosphate,diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethylphosphate, and dibutyl-2-acryloyloxyethyl phosphate.

Among the anionic monomers, an unsaturated carboxylic acid monomer ispreferable, and acrylic acid or methacrylic acid is more preferable,from the viewpoints of dispersion stability, ejection property, and thelike.

(Styrenic Macromer (d))

The styrenic macromer (d) (hereinafter sometimes simply referred to as“macromer”) is used with a view to increasing the affinity for acolorant (particularly, a pigment), thereby increasing the dispersionstability of water-insoluble polymer particles containing a pigment. Thestyrenic macromer (d) may be, for example, a macromer that is a monomerhaving a number average molecular weight of from 500 to 100,000, morepreferably from 1,000 to 10,000, and having a polymerizable functionalgroup, such as an unsaturated group, at one terminal thereof. Themacromer as the (d) component is preferably capable of forming ahydrophobic graft chain, from the viewpoint of increasing the affinityfor a pigment.

The number-average molecular weight of the (d) component may be obtainedby gel permeation chromatography in which polystyrene is used as astandard substance, and tetrahydrofuran containing 50 mmol/L of aceticacid is used as a solvent.

The term “styrenic macromer” refers to a macromer including a structuralunit derived from a styrene-containing monomer such as styrene,α-methylstyrene, or vinyltoluene. From among styrene-containingmonomers, styrene is preferable. The styrenic macromer may be, forexample, a styrene homopolymer having a polymerizable functional groupat one terminal thereof, or a copolymer of styrene and at least oneother monomer wherein the copolymer has a polymerizable functional groupat one terminal thereof. The polymerizable functional group that ispresent at one terminal of the macromer is preferably an acryloyloxygroup or a methacryloyloxy group. A water-insoluble graft polymerincluding a structural unit derived from a styrenic macromer can beobtained by copolymerization using the styrenic macromer as acopolymerization component.

The content of structural units derived from styrenic monomers in thestyrene macromer is preferably 60% by mass or higher, more preferably70% by mass or higher, and particularly preferably 90% by mass orhigher, from the viewpoint of pigment dispersion property.

The styrene macromer may be a commercially-available product, examplesof which include AS-6, AS-6S, AN-6, AN-6S, HS-6, and HS-6S (all of whichare trade names, manufactured by To a Gosei Co., Ltd.).

(Hydrophobic Monomer (e))

A hydrophobic monomer (e) may be used from the viewpoints of, forexample, improving the dispersion stability of the water-resistantcolorant and reducing the amount of free polymers. Examples thereofinclude an alkyl (meth)acrylate, an alkyl (meth)acrylamide, anaromatic-ring-containing monomer (a monomer that includes an aromaticring), and a monomer capable of forming a repeating unit represented bythe Formula (1)-A or (2) below and compounds thereof.

Examples of the alkyl (meth)acrylate include (meth)acrylic esters havingan alkyl group having from 1 to 22 carbon atoms, such as methyl(meth)acrylate, ethyl (meth)acrylate, (iso)propyl (meth)acrylate, (isoor tertiary-)butyl (meth)acrylate, (iso)amyl (meth)acrylate,cyclohexyl(meth)acrylate, 2-ethylhexyl (meth)acrylate, (iso)octyl(meth)acrylate, (iso)decyl (meth)acrylate, (iso)dodecyl (meth)acrylate,and (iso)stearyl(meth)acrylate.

Examples of the alkyl (meth)acrylamide include (meth)acrylamides havingan alkyl group having from 1 to 22 carbon atoms, such as methyl(meth)acrylamide, dimethyl (meth)acrylamide, diethyl (meth)acrylamide,dibutyl (meth)acrylamide, t-butyl (meth)acrylamide, octyl(meth)acrylamide, and dodecyl (meth)acrylamide.

Examples of the aromatic-ring-containing monomer include styrenicmonomers such as styrene, 2-methylstyrene, and vinyltoluene; aryl estersof (meth)acrylic acid such as benzyl (meth)acrylate and phenoxyethyl(meth)acrylate, and vinyl monomers having an aromatic hydrocarbon grouphaving from 6 to 22 carbon atoms, such as ethyl vinyl benzene, 4-vinylbiphenyl, 1,1-diphenylethylene, vinyl naphthalene, and chlorostyrene.

The expression “(iso or tertiary-)” as used herein means iso- ortertiary- or normal-. The expression “(iso)” as used herein means iso-or normal-. Furthermore, the scope of “(meth)acrylate” includes both ofacrylate and methacrylate.

In Formula (1)-A or (2), R¹ represents a hydrogen atom or a substituent.One of R² to R⁵ represents a single bond connected to W, and the othersof R² to R⁵ each independently represent a hydrogen atom or asubstituent. J represents *—CO—, *—COO—, *—CONR¹⁰—, *—COO—, a methylenegroup, a phenylene group, or *—C₆H₄CO—. R¹⁰ represents a hydrogen atom,an alkyl group, an aryl group, or an aralkyl group. W represents asingle bond or a divalent linking group. A¹ represents a heterocyclicgroup. Q¹ represents an atomic group necessary for forming a ringtogether with the carbon atoms. The * sign represents a site connectedto the main chain.

Examples of substituents that R¹ to R⁵ may represent include monovalentsubstituents. Examples of the monovalent substituents (hereinafter,referred to as substituent Z) include an alkyl group, a cycloalkylgroup, an alkenyl group, an alkynyl group, an aryl group, an aminogroup, an alkoxy group, an aryloxy group, a heterocyclyloxy group, anacyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, anacyloxy group, an acylamino group, an alkoxycarbonylamino group, anaryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, acarbamoyl group, an alkylthio group, an arylthio group, aheterocyclylthio group, a sulfonyl group, a sulfinyl group, a ureidogroup, a phosphoric acid amide group, a hydroxyl group, a mercaptogroup, a halogen atom, a cyano group, a sulfo group, a carboxyl group,an oxo group, a nitro group, a hydroxamic acid group, a sulfino group, ahydrazino group, an imino group, a heterocyclic group, a silyl group,and a silyloxy group. These groups may themselves be substituted by oneor more substituents selected from the above substituents Z.

Among the above, R¹ preferably represents a hydrogen atom, an alkylgroup (an alkyl group having preferably from 1 to 30 carbon atoms, morepreferably from 1 to 20 carbon atoms, and particularly preferably from 1to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl,n-octyl, n-decyl, or n-hexadecyl), or an aryl group (an aryl grouphaving preferably from 6 to 30 carbon atoms, more preferably from 6 to20 carbon atoms, and particularly preferably from 6 to 12 carbon atoms,such as phenyl, p-methylphenyl, naphthyl, or anthranyl). R¹ morepreferably represents a hydrogen atom or an alkyl group.

One of R² to R⁵ represents a single bond connected to W, and the othersof R² to R⁵ each independently represent preferably a hydrogen atom, analkyl group (an alkyl group having preferably from 1 to 30 carbon atoms,more preferably from 1 to 20 carbon atoms, and particularly preferablyfrom 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl,tert-butyl, n-octyl, n-decyl, or n-hexadecyl), an aryl group (an arylgroup having preferably from 6 to 30 carbon atoms, more preferably from6 to 20 carbon atoms, and particularly preferably from 6 to 12 carbonatoms, such as phenyl, p-methylphenyl, naphthyl, or anthranyl), an aminogroup (an amino group having preferably from 0 to 30 carbon atoms, morepreferably from 0 to 20 carbon atoms, and particularly preferably from 0to 10 carbon atoms, such as amino, methylamino, dimethylamino,diethylamino, dibenzylamino, diphenylamino, or ditolylamino), an alkoxygroup (an alkoxy group having preferably from 1 to 30 carbon atoms, morepreferably from 1 to 20 carbon atoms, and particularly preferably from 1to 10 carbon atoms, such as methoxy, ethoxy, butoxy, or2-ethylhexyloxy), an aryloxy group (an aryloxy group having preferablyfrom 6 to 30 carbon atoms, more preferably from 6 to 20 carbon atoms,and particularly preferably from 6 to 12 carbon atoms, such asphenyloxy, 1-naphthyloxy, or 2-naphthyloxy), an acyl group (an acylgroup having preferably from 1 to 30 carbon atoms, more preferably from1 to 20 carbon atoms, and particularly preferably from 1 to 12 carbonatoms, such as acetyl, benzoyl, formyl, or pivaloyl), an alkoxycarbonylgroup (an alkoxycarbonyl group having preferably from 2 to 30 carbonatoms, more preferably from 2 to 20 carbon atoms, and particularlypreferably from 2 to 12 carbon atoms, such as methoxycarbonyl orethoxycarbonyl), an aryloxycarbonyl group (an aryloxycarbonyl grouphaving preferably from 7 to 30 carbon atoms, more preferably from 7 to20 carbon atoms, and particularly preferably from 7 to 12 carbon atoms,such as phenyloxycarbonyl), an acyloxy group (an acyloxy group havingpreferably from 1 to 30 carbon atoms, more preferably from 1 to 20carbon atoms, and particularly preferably from 1 to 10 carbon atoms,such as acetoxy or benzoyloxy), an acylamino group (an acylamino grouphaving preferably from 1 to 30 carbon atoms, more preferably from 1 to20 carbon atoms, and particularly preferably from 1 to 10 carbon atoms,such as acetylamino or benzoylamino), an alkoxycarbonylamino group (analkoxycarbonylamino group having preferably from 2 to 30 carbon atoms,more preferably from 2 to 20 carbon atoms, and particularly preferablyfrom 2 to 12 carbon atoms, such as methoxycarbonylamino), anaryloxycarbonylamino group (an aryloxycarbonylamino group havingpreferably from 7 to 30 carbon atoms, more preferably from 7 to 20carbon atoms, and particularly preferably from 7 to 12 carbon atoms,such as phenyloxycarbonylamino), a sulfonylamino group (a sulfonylaminogroup having preferably from 1 to 30 carbon atoms, more preferably from1 to 20 carbon atoms, and particularly preferably from 1 to 12 carbonatoms, such as methanesulfonylamino or benzenesulfonylamino), acarbamoyl group (a carbamoyl group having preferably from 1 to 30 carbonatoms, more preferably from 1 to 20 carbon atoms, and particularlypreferably from 1 to 12 carbon atoms, such as carbamoyl,methylcarbamoyl, diethylcarbamoyl, or phenylcarbamoyl), a sulfonyl group(a sulfonyl group having preferably from 1 to 30 carbon atoms, morepreferably from 1 to 20 carbon atoms, and particularly preferably from 1to 12 carbon atoms, such as mesyl or tosyl), a hydroxyl group, a halogenatom (for example, a fluorine atom, a chlorine atom, a bromine atom, oran iodine atom; more preferably, a fluorine atom), a cyano group, acarboxyl group, a nitro group, or a heterocyclic group;

further more preferably a hydrogen atom, an alkyl group, an aryl group,an amino group, an alkoxy group, an aryloxy group, an acyl group, anacylamino group, a sulfonylamino group, a carbamoyl group, a sulfonylgroup, a hydroxyl group, a halogen atom, or a cyano group, and stillfurther preferably a hydrogen atom, an acyl group, a hydroxyl group, ahalogen atom, or a cyano group.

In Formulae (1)-A and (2), J preferably represents *—CO—, *—CONR¹⁰—, aphenylene group, or *—C₆H₄CO—, and more preferably *—C₆H₄CO—. R¹⁰represents a hydrogen atom, an alkyl group, an aryl group, or an aralkylgroup, and preferably represents a hydrogen atom, an alkyl group, or anaryl group. Preferable definitions of the alkyl group and the aryl groupare the same as the preferable definitions of the alkyl group and thearyl group described in the explanation of the substituents Z,respectively.

In Formulae (1)-A and (2), W represents a single bond or a divalentlinking group.

Examples of the divalent linking group include an imino group, a liner,branched, or cyclic alkylene group (having preferably from 1 to 30carbon atoms, more preferably from 1 to 12 carbon atoms, and furthermore preferably from 1 to 4 carbon atoms, examples of which include amethylene group, an ethylene group, a propylene group, a butylene group,a pentylene group, a hexylene group, an octylene group, and a decylenegroup), an aralkylene group (having preferably from 7 to 30 carbonatoms, and more preferably from 7 to 13 carbon atoms, examples of whichinclude a benzylidene group and a cinnamylidene group), an arylene group(having preferably from 6 to 30 carbon atoms, and more preferably from 6to 15 carbon atoms, examples of which include a phenylene group, acumenylene group, a mesitylene group, a tolylene group, and a xylylenegroup), *—(CR¹¹R¹²)_(n)NHCONH—, and *—(CR¹¹R¹²)_(n)CONH—, in which *indicates a site connected to the main chain, and R¹¹ and R¹² eachindependently represent a hydrogen atom or a substituent, preferably ahydrogen atom, an alkyl group, a halogen atom, or a hydroxyl group, morepreferably a hydrogen atom or an alkyl group, and further morepreferably a hydrogen atom. When plural R¹¹'s and R¹²'s are present,plural R¹¹'s may be the same as or different from each other, and pluralR¹²'s may be the same as or different from each other. Furthermore, nrepresents a positive integer, preferably an integer of from 1 to 10,and more preferably an integer of from 2 to 5. Among those describedabove, *—(CR¹¹R¹²)_(n)NHCONH—, *—(CR¹¹R¹²)_(n)CONH—, or an imino groupis preferable, and an imino group is more preferable.

W preferably represents a single bond, an alkylene group, or an arylenegroup, and more preferably represents a single bond or an alkylenegroup. W is even more preferably a single bond. W may further have asubstituent, and the definition and specifics of the substituent are thesame as those of the substituents Z described above. W may represent agroup formed from a combination of at least two of the divalent linkinggroups described above. It is preferable that W has an ether bondtherein.

In Formula (1)-A, A¹ represents a heterocyclic group. The “heterocyclicgroup” or “heterocyclyl group” refers to a monovalent group obtained byremoving one hydrogen atom from a heterocyclic compound.

The heterocyclic group represented by A¹ is preferably a heterocyclicgroup capable of forming a colorant (especially, a pigment). Thepresence of a heterocyclic group having a high affinity for a pigmentdue to a Van-der-Waals interaction provides the polymer with favorableadsorptivity to pigment, whereby a stable dispersion is obtained.

A heterocyclic compound for forming the heterocyclic group is preferablya compound having at least one hydrogen bonding group in a moleculethereof, and examples thereof include thiophene, furan, xanthene,pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, indole,quinoline, carbazole, acridine, acridone, quinacridon, anthraquinone,phthalimide, quinaldine, and quinophthalone. Of these, benzimidazolone,indole, quinoline, carbazole, acridine, acridone, anthraquinone, andphthalimide are particularly preferable.

The heterocyclic group is particularly preferably a heterocyclic groupthat is similar to the pigment to be used. Specifically, it isparticularly preferable to use at least one selected from acridone andanthraquinone when a quinacridon pigment is used. In such a case,adsorption between the water-insoluble polymer and the colorant isstrong, and detachment of the polymer from the colorant is suppressedregardless of the kind or amount of solvent used as the ink solvent.

In Formula (2), Q¹ represents an atomic group necessary for forming aring together with the carbon atoms (specifically, the two carbon atomsof —C═C—). The atomic group may consist of carbon, nitrogen, oxygen,silicon, phosphorus, and/or sulfur, preferably carbon, nitrogen, oxygen,and/or sulfur, more preferably carbon, nitrogen, and/or oxygen, and evenmore preferably carbon and/or nitrogen. Q¹ which is formed by the atomicgroup may be saturated or unsaturated. In a case in which Q¹ is capableof being substituted, Q¹ may have a substituent. In this case, thedefinition and specifics of the substituent are the same as thedefinition and specifics of the substituent Z above.

In Formula (2), examples of the cyclic structure group connected to W (acyclic structure group constituted by the aryl group having R² to R⁵ andQ¹) include a cyclic structure group which is represented by any one ofthe following Formulae (i) to (vi), and which may have a substituent. InFormulae (i) to (vi), the * sign represents a site connected to W. Amongthem, a cyclic structure group which is represented by the followingFormula (i), (ii), or (iii), and which may have a substituent arepreferable, and a cyclic structure group represented by the followingFormula (i) which may have a substituent is more preferable.

The structural unit (repeating unit) represented by Formula (2) ispreferably a repeating unit represented by the following Formula (3).

In Formula (3), R⁶ to R⁹ each independently represent a hydrogen atom ora substituent. R¹ to R⁵, J, and W have the same definitions andpreferable definitions as R¹ to R⁵, J, and W in Formula (2),respectively.

When any of R⁶ to R⁹ represents a substituent, examples of thesubstituent include those described in the explanation of thesubstituents Z. R⁶ to R⁹ each independently represent preferably ahydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxygroup, an aryloxy group, an acyl group, an alkoxycarbonyl group, anaryloxycarbonyl group, an acyloxy group, an acylamino group, analkoxycarbonylamino group, an aryloxycarbonylamino group, asulfonylamino group, a carbamoyl group, a sulfonyl group, a hydroxylgroup, a halogen atom, a cyano group, a carboxyl group, a nitro group,or a heterocyclic group; more preferably a hydrogen atom, an alkylgroup, an aryl group, an amino group, an alkoxy group, an aryloxy group,an acyl group, an acylamino group, a sulfonylamino group, a carbamoylgroup, a sulfonyl group, a hydroxyl group, a halogen atom, or a cyanogroup; furthermore preferably a hydrogen atom, an acyl group, a hydroxylgroup, a halogen atom, or a cyano group; and particularly preferably ahydrogen atom.

In the repeating unit represented by Formula (3), the combination ofsubstituents is preferably the following combination (a), (b), (c), or(d), more preferably a combination (b), (c), or (d), even morepreferably combination (c) or (d), and particularly preferablycombination (d).

Combination (a): J represents *—CO—, *—CONR¹⁰—, a phenylene group, or*—C₆H₄CO—, in which R¹⁰ represents a hydrogen atom, an alkyl group, oran aryl group. W represents a single bond, an imino group, an alkylenegroup, or an arylene group. R¹ represents a hydrogen atom, an alkylgroup, or an aryl group. R² to R⁵ each independently represent a singlebond, a hydrogen atom, an alkyl group, an aryl group, an amino group, analkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group,an aryloxycarbonyl group, an acyloxy group, acylamino group,alkoxycarbonylamino group, an aryloxycarbonylamino group, asulfonylamino group, a carbamoyl group, a sulfonyl group, a hydroxylgroup, a halogen atom, a cyano group, a carboxyl group, a nitro group,or a heterocyclic group, provided that one of R² to R⁵ represents asingle bond connected to W. R⁶ to R⁹ each independently represent ahydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxygroup, an aryloxy group, an acyl group, an alkoxycarbonyl group, anaryloxycarbonyl group, an acyloxy group, an acylamino group, analkoxycarbonylamino group, an aryloxycarbonylamino group, asulfonylamino group, a carbamoyl group, a sulfonyl group, a hydroxylgroup, a halogen atom, a cyano group, a carboxyl group, a nitro group,or a heterocyclic group.

Combination (b): J represents *—C₆H₄CO—, *—CONR¹⁰—, or a phenylenegroup, and R¹⁰ represents a hydrogen atom or an alkyl group. Wrepresents an imino group, a single bond, or an arylene group. R¹represents a hydrogen atom or an aryl group. R² to R⁵ each independentlyrepresent a hydrogen atom, an alkyl group, an aryl group, an aminogroup, an alkoxy group, an aryloxy group, an acyl group, an acylaminogroup, a sulfonylamino group, a carbamoyl group, a sulfonyl group, ahydroxyl group, a halogen atom, or a cyano group, provided that one ofR² to R⁵ represents a single bond connected to W. R⁶ to R⁹ eachindependently represent a hydrogen atom, an alkyl group, an aryl group,an amino group, an alkoxy group, an aryloxy group, an acyl group, anacylamino group, a sulfonylamino group, a carbamoyl group, a sulfonylgroup, a hydroxyl group, a halogen atom, or a cyano group.

Combination (c): J represents *—C₆H₄CO— or *—CONR¹⁰—, and R¹⁰ representsa hydrogen atom. W represents an imino group or a single bond. R¹represents a hydrogen atom or an aryl group. R² to R⁵ each independentlyrepresent a hydrogen atom, an acyl group, a hydroxyl group, a halogenatom, or a cyano group, provided that one of R² to R⁵ represents asingle bond connected to W. R⁶ to R⁹ each independently represent ahydrogen atom, an acyl group, a hydroxyl group, a halogen atom, or acyano group.

Combination (d): J represents *—C₆H₄CO—. W represents an imino group. R¹represents a hydrogen atom or an aryl group. R² to R⁵ each independentlyrepresent a hydrogen atom, an acyl group, a hydroxyl group, a halogenatom, or a cyano group, provided that one of R² to R⁵ represents asingle bond connected to W. R⁶ to R⁹ each represent a hydrogen atom.

Specific examples of the repeating unit represented by Formula (1)-Ainclude, but are not limited to, those shown below.

Specific examples of the repeating unit represented by Formula (2)include, but are not limited to, those shown below

The (e) component is preferably an aromatic-ring-containing monomer, ora monomer capable of forming a heterocycle-containing repeating unitwhen used for formation of the water-insoluble polymer, from theviewpoints of improving the dispersibility of a colorant (especially, apigment) and reducing the amount of free polymer. Among them, the (e)component is more preferably a monomer capable of forming aheterocycle-containing repeating unit when used for the formation of thewater-insoluble polymer described above (this monomer is hereinafterreferred to as “(e-1) component”), from the viewpoints of, for example,improving the dispersibility of a colorant (especially, a pigment) orreducing the amount of free polymer when used in the black inkcomposition of the present invention.

The content of the (e-1) component in the (e) component is preferablyfrom 10% by mass to 100% by mass, and more preferably from 20% by massto 80% by mass, with respect to the total mass of the (e) component,from the viewpoints of, for example, reducing the amount of freepolymer, and improving print density and rubbing resistance.

The aromatic-ring-containing monomer is preferably a styrenic monomer,which is hereinafter referred to as “(e-2) component”, and is morepreferably styrene or 2-methylstyrene. The content of the (e-2)component in the (e) component is preferably from 10% by mass to 100% bymass, and more preferably from 20% by mass to 80% by mass, with respectto the total mass of the (e) component, from the viewpoints of, forexample, improvement in the print density and rubbing resistance.

From the viewpoint of, for example, improvement in the colorantdispersibility, the aromatic-ring-containing monomer is preferable asthe (e) component. In particular, an aryl ester of (meth)acrylic acid,which is hereinafter referred to as “(e-3) component”, is preferable,and a (meth)acrylate having an arylalkyl group having from 7 to 22carbon atoms, preferably from 7 to 18 carbon atoms, and more preferablyfrom 7 to 12 carbon atoms, or a (meth)acrylate having an aryl grouphaving from 6 to 22 carbon atoms, preferably from 6 to 18 carbon atoms,and more preferably from 6 to 12 carbon atoms, is more preferable.Preferable specific examples of such a monomer include benzyl(meth)acrylate and phenoxyethyl (meth)acrylate. The content of the (e-2)component in the (e) component is preferably from 10% by mass to 100% bymass, and more preferably from 20% by mass to 80% by mass, with respectto the total mass of the (e) component, from the viewpoints ofimprovement in the colorant dispersibility and the like.

The (e) components may be used alone, or in combination of two or morethereof. It is preferable to use a combination of the (e-1) componentand the (e-2) component, a combination of the (e-2) component and the(e-3) component, or a combination of the (e-1) component and the (e-3)component. From the viewpoint of reducing free polymer, it is preferableto use a combination of the (e-1) component and the (e-2) component or acombination of the (e-2) component and the (e-3) component, and mostpreferable to use a combination of the (e-1) component and the (e-2)component.

In the present invention, it is preferable that the monomer mixturecontaining the above-described (c), (d), and (e) components furthercontains a hydroxyl group-containing monomer (f) (hereinafter alsoreferred to as an “(f) component”).

The (f) component increases dispersion stability. Examples of the (0component include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl(meth)acrylate, polyethylene glycol (n=2 to 30; n represents an averageaddition mol number of oxyalkylene groups, and the same applieshereinbelow) (meth)acrylate, propylene glycol (n=2 to 30)(meth)acrylate, and poly(ethylene glycol (n=1 to 15)-propylene glycol(n=1 to 15)) (meth)acrylate. Of these, 2-hydroxyethyl (meth)acrylate,polyethylene glycol monomethacrylate, and polypropylene glycol methacrylate are preferable.

The monomer mixture may include a monomer (g) represented by thefollowing Formula (A). The monomer (g) is hereinafter sometimes referredto as “(g) component”.

CH₂═C(R³)COO(R⁴O)_(p)R⁵  Formula (A)

In Formula (A), R³ represents a hydrogen atom or an alkyl group havingfrom 1 to 5 carbon atoms; R⁴ represents a divalent hydrocarbon groupwhich has 1 to 30 carbon atoms and which may have a hetero atom; R⁵represents a monovalent hydrocarbon group which has 1 to 30 carbon atomsand which may have a hetero atom; and p represents an average additionmol number and represents a number of from 1 to 60, preferably from 1 to30.

The (g) component increases ejection stability of an ink composition,and exhibits excellent effects on preventing misdirection of inkdroplets even in continuous printing, and the like.

Examples of the hetero atom which may be included in R⁴ or R⁵ in Formula(A) include a nitrogen atom, an oxygen atom, a halogen atom, and asulfur atom.

Representative examples of the group represented by R⁴ include anaromatic group having from 6 to 30 carbon atoms, a heterocyclic grouphaving from 3 to 30 carbon atoms, and an alkylene group having from 1 to30 carbon atoms, each of which may have a substituent. Representativeexamples of the group represented by R⁵ include an aromatic group havingfrom 6 to 30 carbon atoms, and a heterocyclic group having from 3 to 30carbon atoms, each of which may have a substituent. R⁴ may represent acombination of two or more of these groups, and, similarly, R⁵ mayrepresent a combination of two or more of these groups. Examples of thesubstituent include an aromatic group, a heterocyclic group, an alkylgroup, a halogen atom, and an amino group.

Preferable examples of the group represented by R⁴ include: a phenylenegroup that may have a substituent having from 1 to 24 carbon atoms; analiphatic alkylene group having from 1 to 30 carbon atoms, and morepreferably having from 1 to 20 carbon atoms; an alkylene group which hasat least one aromatic ring bonded thereto and which has from 7 to 30carbon atoms (including the carbon atoms of the at least one aromaticring), and an alkylene group which has at least one heterocycle bondedthereto and which has from 4 to 30 carbon atoms (including the carbonatoms of the at least one heterocycle). Particularly preferable specificexamples of the R⁴O group include an oxyethylene group, anoxy(iso)propylene group, an oxytetramethylene group, anoxyheptamethylene group, an oxyhexamethylene group, an oxyalkylene groupwhich is composed of one or more types of oxyalkylene selected from theabove, and which has from 2 to 7 carbon atoms, and an oxyphenylenegroup.

Specific examples of R⁵ include a phenyl group, an aliphatic alkyl grouphaving from 1 to 30 carbon atoms (preferably an aliphatic alkyl groupwhich has from 1 to 20 carbon atoms and which may be branched), anaromatic-ring-containing alkyl group having from 7 to 30 carbon atoms,and a heterocycle-containing alkyl group having from 4 to 30 carbonatoms. Examples of more preferable R⁵ include an alkyl group having from1 to 12 carbon atoms, such as a methyl group, an ethyl group, aniso-propyl group, a propyl group, an iso-butyl group, a butyl group, aniso-pentyl group, a pentyl group, an iso-hexyl group, or a hexyl group;and a phenyl group.

Specific examples of the (g) component includemethoxypolyethyleneglycol(p in the above Formula (A) being from 1 to 30)(meth)acrylate, methoxypolytetramethyleneglycol(p being from 1 to 30)(meth)acrylate, ethoxypolyethyleneglycol(p being from 1 to 30)(meth)acrylate, (iso)propoxypolyethyleneglycol(p being from 1 to 30)(meth)acrylate, butoxypolyethyleneglycol(p being from 1 to 30)(meth)acrylate, octoxypolyethyleneglycol(p being from 1 to 30)(meth)acrylate, methoxypolypropyleneglycol(p being from 1 to 30)(meth)acrylate, and methoxypoly(ethyleneglycol-co-propyleneglycol)(meth)acrylate (wherein p is from 1 to 30 and the number ofethyleneglycol units is from 1 to 29). From among the above,methoxypolyethyleneglycol(p being from 1 to 30) (meth)acrylate ispreferable.

Specific examples of the (f) and (g) components include polyfunctionalacrylate monomers (NK-ESTER) M-40G, 90G, and 230G (trade names,manufactured by Shin-Nakamura Chemical Co., Ltd.), and BLEMMER seriesproducts including PE-90, 200, and 350, PME-100, 200, 400, and 1000,PP-1000, PP-500, PP-800, AP-150, AP-400, AP-550, AP-800, 50PEP-300,50POEP-800B, and 43PAPE-600B (trade names, manufactured by NOFCORPORATION).

With respect to each of the (a) to (g) components, the component mayeach be used singly, or in combination of two or more thereof.

The contents of the (c) to (e) components in a monomer mixture are asdescribed below.

The content of (c) component is preferably from 1 to 50% by mass, morepreferably from 2 to 40% by mass, and particularly preferably from 3 to20% by mass, from the viewpoint of dispersion stability or the like ofthe water-insoluble polymer particle containing a colorant (especially,pigment) to be obtained.

The content of (d) component is preferably from 1 to 50% by mass, andmore preferably from 5 to 40% by mass, from the viewpoint of dispersionstability or the like of the water-insoluble polymer particle containinga colorant (especially, pigment).

The content of (e) component is preferably from 5 to 98% by mass, andmore preferably from 10 to 60% by mass, from the viewpoint of dispersionstability or the like of the water-insoluble polymer particle containinga colorant (especially, pigment).

A mass ratio of the content of (c) component to the total content of (d)component and (e) component ((c)/[(d)+(e)]) is preferably from 0.01 to1, more preferably from 0.02 to 0.67, and further more preferably from0.03 to 0.50, from the viewpoint of ejection property or the like of anink composition to be obtained.

The content of (d) component is preferably from 5 to 40% by mass, andmore preferably from 7 to 30% by mass, from the viewpoints of ejectionproperty and dispersion stability.

The content of (e) component is preferably from 5 to 50% by mass, andmore preferably from 10 to 40% by mass, from the viewpoints of ejectionproperty, dispersion stability, and the like.

The total content of (c) component and (d) component is preferably from6 to 60% by mass, and more preferably from 10 to 50% by mass, from theviewpoints of dispersion stability in water and the like.

The total content of (c) component and (e) component is preferably from6 to 75% by mass, and more preferably from 13 to 50% by mass, from theviewpoints Of dispersion stability in water, ejection property, and thelike.

The total content of (c) component, (d) component, and (e) component ispreferably from 6 to 60% by mass, and more preferably from 7 to 50% bymass, from the viewpoints of dispersion stability in water and ejectionproperty.

When Polymer [2] has a salt-forming group derived from thesalt-forming-group-containing monomer (c), polymer [2] may be used afterneutralization with a neutralizer . The neutralizer for use may be anacid or a base, depending on the type of salt-forming group contained inthe water-insoluble polymer. Examples of the neutralizer include: acidssuch as hydrochloric acid, acetic acid, propionic acid, phosphoric acid,sulfuric acid, lactic acid, succinic acid, glycolic acid, gluconic acid,and glyceric acid; and bases such as lithium hydroxide, sodiumhydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine,trimethylamine, ethylamine, diethylamine, triethylamine,triethanolamine, tributylamine, tetramethyl ammonium hydroxide, benzyltrimethyl ammonium hydroxide, choline hydroxide, and tetrabutyl ammoniumhydroxide. The neutralization degree of the water-insoluble polymer ispreferably from 10 to 200%, more preferably from 20 to 150%, andparticularly preferably from 50 to 150%.

When the salt-forming group is an anionic group, the neutralizationdegree can be obtained according to the following equation:

When the salt-forming group is an anionic group, the neutralizationdegree is calculated from the following equation:

neutralization degree (%)={[mass of neutralizing agent (g)/equivalentweight of neutralizing agent]/[acid value of polymer (KOHmg/g)×mass ofpolymer (g)/(56×1,000)]}×100

When the salt-forming group is a cationic group, the neutralizationdegree is calculated from the following equation:

neutralization degree (%)={[mass of neutralizing agent (g)/equivalentweight of neutralizing agent]/[amine value of polymer (HCLmg/g)×mass ofpolymer (g)/(36.5×1,000)]}×100

The acid value or amine value may be obtained by calculation based onthe types and ratios of structural unit contained in the water-insolublevinyl polymer, or by titration after dissolving the polymer in anappropriate solvent (for example, methyl ethyl ketone).

The acid value of the water-insoluble resin in the invention ispreferably from 30 mgKOH/g to 100 mgKOH/g, more preferably from 30mgKOH/g to 85 mgKOH/g, and particularly preferably from 50 mgKOH/g to 85mgKOH/g, from the viewpoints of pigment dispersibility and storagestability.

The acid value as used herein is defined as the mass (mg) of KOHnecessary for completely neutralizing 1 g of the water-insoluble resin,and is determined by a method according to the method described inJapanese Industrial Standards (JIS) (JIS K0070 (1992), which isincorporated herein by reference).

The molecular weight of the water-insoluble resin in the invention, interms of weight average molecular weight (Mw), is preferably 30,000 ormore, more preferably from 30,000 to 150,000, still more preferably from30,000 to 100,000, and particularly preferably from 30,000 to 80,000.When the molecular weight is 30,000 or more, steric repulsion effects asa dispersant can be improved, and the water-insoluble resin has highertendency to be adsorbed on a pigment due to steric effects.

The number-average molecular weight (Mn) of the water-insoluble resin ispreferably from about 1,000 to 100,000, and particularly preferably fromabout 3,000 to 50,000. A number-average molecular weight of thewater-insoluble resin within the above range is preferable from theviewpoint of exerting a function as a coating film for a pigment or afunction as a coating film for an ink composition. The polymer [1] ispreferably used in the form of a salt of an alkali metal or a salt of anorganic amine.

The molecular weight distribution (weight average molecularweight/number average molecular weight) of the water-insoluble resin inthe invention is preferably in the range of from 1 to 6, and morepreferably in the range of from 1 to 4. When the molecular weightdistribution is within the above range, the dispersion stability and theejection stability of the ink can be heightened.

Number average molecular weight and weight average molecular weight aremeasured with a gel permeation chromatography (GPC). HLC-8020GPC (tradename) manufactured by Tosoh Corporation is used as a GPC instrument.Three columns of TSKGEL SUPER MULTIPORE HZ-H (trade name, 4.6 mmID×15cm) manufactured by Tosoh Corporation are used as the columns. THF(tetrahydrofuran) is used as an eluent. Molecular weight can be obtainedby conversion using polystyrne as a standard substance.

The water-insoluble resin in the invention can be synthesized by variouspolymerization methods, such as solution polymerization, precipitationpolymerization, suspension polymerization, bulk polymerization, andemulsion polymerization. The polymerization reaction can be performedusing a known procedure, such as in a batch manner, a semi-continuousmanner, or a continuous manner. The method of initiating polymerizationmay be, for example, a method using a radical initiator or a method ofirradiating light or a radiation. Polymerization methods andpolymerization initiation methods are described in, for example, TeijiTsuruta, “Kobunshi Gosei-Houhou (Polymer Synthesis Method)”, revisededition, (NIKKAN KOGYO SHINBUN LTD., 1971) and Takayuki Otsu andMasayoshi Kinoshita, “Kobunshi-Gosei no Jikkenho (Experimental Techniqueof Polymer Synthesis)”, (Kagaku-dojin Publishing Company Inc., 1972),pp. 124 to 154.

Among the polymerization methods, a solution polymerization method inwhich a radical initiator is used is particularly preferable. Examplesof a solvent used in the solution polymerization method include variousorganic solvents such as ethyl acetate, butyl acetate, acetone, methylethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran,dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, benzene, toluene,acetonitrile, methylene chloride, chloroform, dichloroethane, methanol,ethanol, 1-propanol, 2-propanol, or 1-butanol. The solvents may be usedalone, or in combination of two or more thereof. Alternatively, amixture thereof with water may be used. The polymerization temperatureshould be adjusted in consideration of the molecular weight of thepolymer to be produced, the kind of initiator, or the like. Thepolymerization temperature is usually from about 0 to 100° C., and it ispreferable that polymerization is carried out at a temperature within arange from 50 to 100° C. The reaction pressure may be appropriatelyselected, and is usually from 1 to 100 kg/cm², and particularlypreferably from about 1 to 30 kg/cm². The reaction time may be fromabout 5 hours to 30 hours, in general. The obtained resin may besubjected to purification such as re-precipitation.

The mass ratio between carbon black (CB) and water-insoluble resin (r)(CB:r) in the resin-coated CB is preferably in the range of from 100:25to 100:140, and more preferably in the range of from 100:25 to 100:50.With respect to the ratio (CB:r), when the amount of water-insolubleresin is equal to or greater than a ratio of 100:25, dispersionstability and resistance against rubbing tend to improve. When theamount of water-insoluble resin is equal to or smaller than a ratio of100:140, dispersion stability tends to improve.

The particle diameter (volume average diameter) of the dispersion of theresin-coated CB is preferably from 50 to 120 nm, more preferably from 60to 100 nm, and still more preferably from 70 to 90 nm. When the particlediameter is 50 nm or more, deterioration of stability tends to besuppressed. When the particle diameter is 120 nm or less, ejectionproperties tend to improve, and occurrence of white dot defects in therecorded image tends to be suppressed. Therefore, the particle diameterrange of from 50 nm to 120 nm is preferable.

The particle size distribution of the particle diameter is notparticularly limited, and may be wide or monodispersed. A mixture of twoor more of dispersions each having a monodispersed particle sizedistribution may be used.

The particle diameter of the resin-coated CB dispersion is a valuemeasured by a dynamic light scattering method using a Nanotrac particlesize distribution analyzer UPA-EX 150 (trade name, manufactured byNikkiso Co., Ltd.).

The resin-coated CB can be produced by a conventional physical orchemical method, using a water-insoluble resin, carbon black, and thelike. For example, the resin-coated CB can be produced by the methoddescribed in JP-A No. 9-151342, JP-A No. 10-140065, JP-A No. 11-209672,JP-A No. 11-172180, JP-A No. 10-25440, or JP-A No. 11-43636. Specificexamples of the production method include a phase inversionemulsification method and an acid precipitation method described in JP-ANo. 9-151342 and JP-A No. 10-140065.

When the resin-coated CB is a particle obtained by coating carbon blackwith a water-insoluble resin, the resin-coated CB is preferably a carbonblack coated with a water-insoluble resin by a phase inversionemulsification method, from the viewpoint of the dispersion stability.

The phase inversion emulsification method is basically a self-dispersing(phase inversion emulsification) method in which a mixed product of aresin having a self-dispersibility or solubility and a pigment isdispersed in water. The mixed product may further include the curingagent or polymer compound. The scope of the mixed product as used hereinencompasses a state in which the components thereof are only mixed witheach other without dissolving in each other, a state in which thecomponents thereof are mixed with each other and dissolved in eachother, and a state in which both of these states are present. An exampleof a specific production method by a “phase inversion emulsification” isa method disclosed in JP-A No. 10-140065.

Examples of specific production methods involving a phase inversionemulsification or an acid deposition method include methods disclosed inJP-A No. 9-151342 and JP-A No. 10-140065.

In the invention, the resin-coated CB included in the ink compositionmay be produced through a preparation step of preparing a dispersion ofa resin-coated CB (pigment) by a method which includes the followingsteps (1) and (2) and which uses a water-insoluble resin. The black inkcomposition of the invention may be produced by forming an aqueous inkby using the dispersion of a resin-coated CB obtained in the preparationstep, together with water and an organic solvent.

Step (1): a step in which a mixture including a water-insoluble resin,an organic solvent, a neutralizer, carbon black, and water is subjectedto a dispersion treatment such as agitation, thereby obtaining adispersion.

Step (2): a step in which the organic solvent is removed from thedispersion.

The agitation method is not particularly limited, and a generally-usedmixing and agitation apparatus or a disperser such as an ultrasonicdisperser, a high-pressure homogenizer, or a bead mill may be used, asnecessary.

Preferable examples of the organic solvent include alcohol solvents,ketone solvents, and ether solvents. The specifics of thereof aredescribed in the item of water-insoluble resin particles describedbelow. The neutralizer is used in order to neutralize some or all of thedissociative groups of the polymer so as to allow the specific copolymerto get into a stable emulsion or dispersion state in water. Thespecifics of the neutralizer are described below.

In the process (2), the organic solvent is removed from the dispersionobtained through the process (1), by a common method such asdistillation under reduced pressure, whereby phase inversion into anaqueous system occurs, and a dispersion of resin-coated pigmentparticles, each of which is composed of a pigment particle and acopolymer that covers the surface of the pigment particle, is obtained.The organic solvent has substantially been removed from the obtainedaqueous dispersion, and the amount of residual organic solvent ispreferably 0.2% by mass or less, and more preferably 0.1% by mass orless.

More specifically, the method includes, for example: (1) a step ofmixing a copolymer having an anionic group or a solution obtained bydissolving the copolymer in an organic solvent, with a basic compound(i.e., neutralizing agent) for neutralization; (2) a step of mixing theresultant mixture with a pigment to produce a suspension, and dispersingthe pigment using a disperser or the like to obtain a pigmentdispersion; and (3) a step of removing the organic solvent bydistillation or the like, thereby coating the pigment with the specificcopolymer having an anionic group and dispersing the pigment in anaqueous medium, to obtain an aqueous dispersion.

More specifically, the disclosures of JP-A No. 11-209672 and JP-A No.11-172180 may be referred to.

In the invention, the dispersion treatment may be carried out using aball mill, a roll mill, a bead mill; a high-pressure homogenizer, ahigh-speed stirring dispersion apparatus, an ultrasonic homogenizer, orthe like.

The content ratio of carbon black (excluding the water-insoluble resincovering the carbon black) in the black ink composition of the inventionis from 1.0 to 2.0% by mass with respect to the total mass of the blackink composition. When the content ratio of carbon black is less than1.0% by mass, the content of carbon black is too small, and a desiredblack density is not maintained. When the content ratio of carbon blackexceeds 2.0% by mass, streak-shaped unevenness in image tends to begenerated, and damage to a head nozzle surface during maintenance is notprevented.

Specifically, from the viewpoints of preventing generation ofstreak-shaped unevenness in an image and generation of damage to a headnozzle, the content ratio of carbon black is more preferably from 1.2 to1.8% by mass, and particularly preferably from 1.3 to 1.7% by mass.

(Resin-Coated Cyan Pigment)

The black ink composition of the invention further includes at least onecyan pigment at least a part of the surface of which is coated with awater-insoluble resin (which may be referred to as “resin-coated cyanpigment” hereinbelow). The resin-coated cyan pigment is a particle inwhich a cyan pigment is partially or entirely coated with awater-insoluble resin, and is included in a dispersed state in the inkcomposition.

—Cyan Pigment—

Examples of the cyan pigment include C. I. Pigment Blue 1, 2, 3, 15,15:1, 15:2, 15:3, 15:34, 16, 17:1, 22, 25, 56, and 60, and C.I. Vat Blue4, 60, and 63. (Copper) phthalocyanine pigments are preferable, and C.I.Pigment Blue 15:3 is particularly preferable. These pigments may be usedsingly, or in mixture of two or more thereof at arbitrary proportions.

—Water-insoluble Resin—

Examples of the water-insoluble resin with which the cyan pigment iscoated include the above-described examples of the water-insoluble resinwith which the carbon black is coated. Specific examples thereof include[1] a polymer containing a repeating unit (a) represented by theabove-mentioned Formula (1) and a repeating unit (b) having an ionicgroup (preferably, a repeating unit having a structural unit derivedfrom an alkyl (meth)acrylate), and [2] a polymer containing a structuralunit derived from a salt-forming group-containing monomer (c) and atleast one structural unit derived from a styrene macromer (d) and/or ahydrophobic monomer (e), and preferable embodiments thereof are also thesame as the preferable embodiments of these polymers described above.

The term “insoluble” as used in this context means that, when a polymeris mixed with an aqueous medium at 25° C., the amount of the polymerdissolved therein is 15% by mass or less with respect to the totalpolymer mixed in the aqueous medium. From the viewpoints of furtherimproving rubbing resistance and preventing color transfer betweenmedia, the amount of the dissolved polymer is preferably 10% by mass orless with respect to the total polymer. The details of the polymers [1]and [2] are described above.

From the viewpoint of dispersion stability, the resin-coated cyanpigment are preferably prepared by coating a cyan pigment with awater-insoluble resin by a phase inversion emulsification method. Thephase inversion emulsification method is as described above.

The content ratio of cyan pigment in the black ink composition of theinvention is preferably from 1 to 50% by mass with respect to the CB.When the content ratio of cyan pigment is 1% by mass or higher, a colorchange (yellowing) caused by reduction in the amount of carbon black iscompensated, and a desired color and a desired color density aremaintained. When the content ratio of cyan pigment is 50% by mass orless, the amount of cyan pigment is not excessively high relative tocarbon black, and a desired black hue can be obtained.

Specifically, from such viewpoints, the content ratio of cyan pigment ispreferably from 10 to 45% by mass, and further more preferably from 20to 40% by mass, with respect to the CB.

(Resin-Coated Magenta Pigment)

The black ink composition of the invention further includes at least onemagenta pigment at least a part of the surface of which is coated with awater-insoluble resin (which may be referred to as “resin-coated magentapigment” hereinbelow). The resin-coated magenta pigment is a particle inwhich a magenta pigment is partially or entirely coated with awater-insoluble resin, and is included in a dispersed state in the inkcomposition.

—Magenta Pigment—

Examples of the magenta pigment include azo pigments, disazo pigments,azo lake pigments, quinacridone pigments, perylene pigments, andanthraquinone pigments.

Specific examples of preferable magenta pigment include C.I. Pigment Red48, 57, 122, 184, and 188, and C.I. Pigment Violet 19. A quinacridonpigment is preferable, and C.I. Pigment Red 122 and C.I. Pigment Violet19 are particularly preferable. The pigments may be used singly.Alternatively, a mixture of two or more of the above pigments atarbitrary proportions may be used, or a solid solution of two or more ofthe above pigments may be used.

—Water-insoluble Resin—

Similarly to the case of the cyan pigment, the specifics and examples ofthe water-insoluble resin with which the magenta pigment is coated arethe same as the above-described specifics and examples of thewater-insoluble resin with which the carbon black is coated.

Specific examples thereof include [1] a polymer containing a repeatingunit (a) represented by the Formula (1) described above and a repeatingunit (b) having an ionic group (preferably a repeating unit derived froman alkyl (meth)acrylate), and [2] a polymer containing a structural unitderived from a salt-forming group-containing monomer (c) and at leastone structural unit derived from a styrene macromer (d) and/or ahydrophobic monomer (e), and preferable embodiments thereof are also thesame as the preferable embodiments of these polymers described above.

The term “insoluble” as used in this context means that, when a polymeris mixed with an aqueous medium at 25° C., the amount of the polymerdissolved therein is 15% by mass or less with respect to the totalpolymer mixed in the aqueous medium. From the viewpoints of furtherimproving rubbing resistance and preventing color transfer betweenmedia, the amount of the dissolved polymer is preferably 10% by mass orless with respect to the total polymer. The details of the polymers [1]and [2] are as described above.

The resin-coated magenta pigment is preferably a magenta pigment coatedwith a water-insoluble resin by a phase inversion emulsification method,from the viewpoint of dispersion stability. Details of the phaseinversion emulsification method are as described above.

When the black ink composition of the invention contains a resin-coatedmagenta pigment, the content ratio of resin-coated magenta pigment inthe black ink composition is preferably from 1 to 70% by mass withrespect to the resin-coated CB. When the content ratio of resin-coatedmagenta pigment is 1% by mass or higher, a color change (yellowing)caused by reduction in the amount of carbon black is compensated, and adesired color and a desired color density are maintained. In addition,since the amount of carbon black can be reduced, significant effectswith respect to prevention of generation of streak-shaped unevenness inan image and prevention of generation of nozzle damage duringmaintenance are exerted. Furthermore, use of the magenta pigmenttogether with carbon black enables reduction in color visibility,whereby color transfer is effectively prevented. When the content ratioof resin-coated magenta pigment is 70% by mass or less, the amount ofmagenta pigment is not excessively high relative to carbon black, and adesired black hue can be obtained.

From such viewpoints, the content ratio of resin-coated magenta pigmentis more preferably from 20 to 65% by mass from the viewpoint ofpreventing a color change in black hue when an intermediate tone is tobe expressed, and further more preferably from 35 to 60% by mass fromthe viewpoints of preventing color transfer.

The water-insoluble resin used for the resin-coated CB, thewater-insoluble resin used for the resin-coated cyan pigment, and thewater-insoluble resin used for the resin-coated magenta pigment may bemutually different polymers which are respectively suitable for therespective pigment structures, or may be the same polymer.

(Resin-Coated Yellow Pigment)

In a preferable embodiment, the black ink composition of the inventionfurther includes at least one yellow pigment at least a part of thesurface of which is coated with a water-insoluble resin (which may bereferred to as “resin-coated yellow pigment” hereinbelow). Theresin-coated yellow pigment is a particle in which a yellow pigment ispartially or entirely coated with a water-insoluble resin, and isincluded in a dispersed state in the ink composition.

—Yellow Pigment—

Examples of the yellow pigment include C.I. Pigment Yellow 1, 2, 3, 4,5, 6, 7, 10, 11, 12, 13, 14, 14C, 16, 17, 24, 34, 35, 37, 42, 53, 55,65, 73, 74, 75, 81, 83, 93, 95, 97, 98, 100, 101, 104, 108, 109, 110,114, 117, 120, 128, 129, 138, 150, 151, 153, 154, 155, and 180. Theyellow pigment may be used singly, or in mixture of two or more thereofat arbitrary proportions, or in combination of a solid solution of twoor more thereof.

—Water-insoluble Resin—

Examples of the water-insoluble resin with which the yellow pigment iscoated include the above-described examples of the water-insoluble resinwith which the carbon black is coated, similarly to the cases of thecyan pigment and magenta pigment.

Specific examples thereof include [1] a polymer containing a repeatingunit (a) represented by the above-described Formula (1) and a repeatingunit (b) having an ionic group (preferably a repeating unit having astructural unit derived from an alkyl (meth)acrylate), and [2] a polymercontaining a structural unit derived from a salt-forminggroup-containing monomer (c) and at least one structural unit derivedfrom a styrene macromer (d) and/or a hydrophobic monomer (e), andpreferable embodiments thereof are also the same as the preferableembodiments of these polymers described above.

The term “insoluble” as used in this context means that, when a polymeris mixed with an aqueous medium at 25° C., the amount of the polymerdissolved therein is 15% by mass or less with respect to the totalpolymer mixed in the aqueous medium. From the viewpoints of furtherimproving rubbing resistance and preventing color transfer betweenmedia, the amount of the dissolved polymer is preferably 10% by mass orless with respect to the total polymer. The details of the polymers [1]and [2] are described above.

The resin-coated yellow pigment is preferably a yellow pigment coatedwith a water-insoluble resin by a phase inversion emulsification method,from the viewpoint of dispersion stability. Details of the phaseinversion emulsification method are as described above.

When the black ink composition of the invention includes a resin-coatedyellow pigment, which is a preferable embodiment of the black inkcomposition of the invention, the content ratio of resin-coated yellowpigment in the black ink composition is preferably from 1 to 70% by masswith respect to the resin-coated CB. When the content ratio ofresin-coated yellow pigment is 1% by mass or higher, a color change(yellowing) caused by reduction in the amount of carbon black iscompensated, and a desired color and a desired color density aremaintained. In addition, since the amount of carbon black is reduced,significant effects with respect to prevention of generation ofstreak-shaped unevenness in an image and prevention of generation ofnozzle damage during maintenance are exerted. When the content ratio ofresin-coated yellow pigment is 70% by mass or less, the amount of yellowpigment is not excessively high relative to carbon black, and a desiredblack hue can be obtained.

Specifically, from such viewpoints, the content ratio of resin-coatedyellow pigment is more preferably from 20 to 65% by mass from theviewpoint of preventing color change in black hue when an intermediatetone is to be expressed, and further more preferably from 35 to 60% bymass from the viewpoints of preventing color transfer.

The water-insoluble resin used for the resin-coated CB, thewater-insoluble resin used for the resin-coated cyan pigment, thewater-insoluble resin used for the resin-coated magenta pigment and thewater-insoluble resin used for the resin-coated yellow pigment may bemutually different polymers that are respectively suitable for therespective pigment structures, or may be the same polymer.

In each of the resin-coated cyan pigment particle, the resin-coatedmagenta pigment particle, and the resin-coated yellow pigment particle,the ratio of cyan pigment (cy), magenta pigment (m/z), or yellow pigment(ye) to water-insoluble resin (r) (i.e., “cy:r”, “m/z:r”, or “ye:r”) ispreferably from 100:25 by mass to 100:140 by mass, and more preferablyfrom 100:25 by mass to 100:60 by mass. Regarding the ratio (i.e.,“cy:r”, “m/z:r”, or “ye:r”) by mass, when the proportion ofwater-insoluble resin is 25 or more relative to 100 parts of pigment,the black ink composition obtained by mixing these pigments hasexcellent dispersion stability and excellent ejection stability. Aproportion of water-insoluble resin of 140 or less relative to 100 partsof pigment is advantageous from the viewpoints of long-term ejectionstability, and easiness in removal and/or cleaning of ink adhered to anozzle member (i.e., excellent maintenance capability).

From the viewpoint of color hue, the ratio (i.e., “cb:(cy+m/z+ye)”) ofthe carbon black (cb) to the total amount (i.e., cy+m/z+ye) of the cyanpigment (cy), magenta pigment (m/z), and yellow pigment (ye), which areincluded in the black ink composition of the invention, is preferablyfrom 100:40 to 100:90 by mass, more preferably from 100:50 to 100:80 bymass, and preferably further satisfies the following expression.

m/z>cy>ye (in terms of mass)

In this case, the ratio (i.e., “cy:m/z”) of the cyan pigment to themagenta pigment is preferably from 100:100 to 100:160 by mass, and morepreferably from 100:120 to 100:140 by mass, from the viewpoints ofobtaining a desired hue and suppressing variation of the hue.

The total amount (mass) of all pigments (excluding coating resins, thesame applies hereinafter) included in the black ink composition of theinvention is from 1.8 to 3.5% by mass with respect to the total amount(mass) of the black ink composition. When the total amount of allpigments is less than 1.8% by mass, a desired color density or hue maynot be obtained. When the total amount of all pigments exceeds 3.5% bymass, streak-shaped unevenness in an image tends to appear, andgeneration of damage to a head nozzle portion during maintenance may notbe avoided.

Specifically, from the viewpoints of further increasing effects withrespect to prevention of generation of streak-shaped unevenness in animage and damage to a nozzle portion, the total amount of all pigmentsrelative to the total amount of the black ink composition is preferablyfrom 2.0 to 3.3% by mass, and more preferably from 2.2 to 3.0% by mass.

(Particles of Water-Insoluble Resin)

The black ink composition according to the invention includes at leastone type of particle of a water-insoluble resin. Inclusion of thewater-insoluble resin particles, in addition to the inclusion of theabove-described resins that cover the pigments, improves the fixabilityof the ink composition to the recording medium and the rubbingresistance of the image. Further, when the treatment liquid describedbelow is used for image formation, the particles aggregate whencontacting the treatment liquid or when contacting an area on which thetreatment liquid has been applied and dried, as a result of which theviscosity of the ink composition increases; thus, the particles servesto fix the ink composition.

The “water-insoluble resin” refers to a polymer of which the dissolutionamount when the polymer is dried at 105° C. for 2 hours and thendissolved in 100 g of water at 25° C. is 10 g or less . The dissolutionamount is preferably 5 g or less, and more preferably 1 g or less, fromthe viewpoint of improving the continuous ejection properties andejection stability of the ink. The dissolution amount is a dissolutionamount when the polymer has been 100% neutralized with either sodiumhydroxide or acetic acid depending on the type of salt-forming groups ofthe water-insoluble polymer.

The water-insoluble resin particles may be particles of a resin of whichexamples include thermoplastic, thermosetting, or modified, acryl-based,epoxy-based, polyurethane-based, polyether-based, polyamide-based,unsaturated polyester-based, phenol-based, silicone-based, orfluorine-containing resins; polyvinyl-based resins, such as vinylchloride, vinyl acetate, polyvinyl alcohol, and polyvinyl butyral;polyester-based resins, such as alkyd resins and phthalic acid resins;amino-based materials, such as melamine resins, melamine-formaldehyderesins, aminonalkyd co-condensate resins, and urea resins; andco-polymers or mixtures thereof. Among them, anionic acryl-based resinscan be obtained by polymerizing, for example, an acrylic monomer havingan anionic group (anionic group-containing acrylic monomer) and,optionally, one or more other monomers that can be copolymerized withthe anionic group-containing acrylic monomer in a solvent. Examples ofthe anionic group-containing acrylic monomer include acrylic monomershaving at least one selected from the group consisting of a carboxylgroup, a sulfonic acid group, and a phosphonic acid group. Among them,preferable examples of the anionic group-containing acrylic monomerinclude acrylic monomers having a carboxyl group (for example, acrylicacid, methacrylic acid, crotonic acid, ethacrylic acid, propylacrylicacid, isopropylacrylic acid, itaconic acid, and fumaric acid), and morepreferable examples of the anionic group-containing acrylic monomersinclude acrylic acid and methacrylic acid.

The water-insoluble resin particles are preferably self-dispersing resinparticles from the viewpoints of ejection stability and the liquidstability (particularly, dispersion stability) of the system containingthe pigment. The self-dispersing resin refers to a water-insolublepolymer that can get into a dispersed state in an aqueous medium due tofunctional groups (particularly, acidic groups or salts thereof) of thepolymer itself, when dispersed by a phase inversion emulsificationmethod in the absence of surfactant.

The term “dispersed state” as used in this context includes anemulsified state (i.e., emulsion) in which the water-insoluble polymeris dispersed in a liquid state in the aqueous medium, and a dispersedstate (i.e., suspension) in which the water-insoluble polymer isdispersed in a solid state in the aqueous medium.

From the viewpoint of ink fixing property when the self-dispersing resinis included in the ink composition, the self-dispersing resin ispreferably a self-dispersing resin that takes a dispersed state in whichthe water-insoluble polymer is dispersed in a solid state.

The method of preparing an emulsified or dispersed state of theself-dispersing resin, e.g., an aqueous dispersion of theself-dispersing resin, may be a phase inversion emulsification method.The phase inversion emulsification method may be, for example, a methodincluding: dissolving or dispersing a self-dispersing resin in a solvent(such as a water-soluble organic solvent); thereafter pouring theresultant into water without adding a surfactant; agitating and mixingthe resultant in a state in which the salt-forming groups (such asacidic groups) that the self-dispersing resin has are neutralized; andremoving the solvent, thereby obtaining an aqueous dispersion in theemulsified or dispersed state.

The following procedure can be used to determine whether awater-insoluble polymer is a self-dispersing resin as mentioned herein:30 g of a water-insoluble polymer is dissolved in 70 g of an organicsolvent (such as methyl ethyl ketone) to form a solution, the solutionis mixed with 200 g of water and a neutralizer that can neutralize thesalt-forming groups of the water-insoluble polymer to a degree of 100%(the neutralizer being sodium hydroxide if the salt-forming groups areanionic, or acetic acid if the salt-forming groups are cationic), themixture is stirred (apparatus: an stirring apparatus having a stirringblade, rotation rate: 200 rpm, 30 minutes, 25° C.), and the organicsolvent is removed from the mixture liquid. If a stable emulsificationor dispersion state of the water-insoluble polymer in the mixture liquidis maintained for at least one week at 25° C. after the removal of theorganic solvent from the mixture liquid, and occurrence of precipitationis not confirmed by visual observation for at least one week at 25° C.after the removal of the organic solvent, the water-insoluble polymer isconsidered to be a self-dispersing resin.

The stability of an emulsification or dispersion state of theself-dispersing resin can be confirmed also by an accelerated test ofprecipitation using centrifugation. In the accelerated test ofprecipitation using centrifugation, the stability can be evaluated by,for example, adjusting the aqueous dispersion of polymer particlesobtained by the above method to a solids concentration of 25% by mass,performing centrifugation at 12,000 rpm for 1 hour, and measuring thesolids concentration of the supernatant after centrifugtion.

When the ratio of the solids concentration after centrifugation to thesolids concentration before centrifugation is large (i.e., is nearly 1),precipitation of polymer particles due to centrifugation does not occur,that is, the aqueous dispersion of polymer particle is relatively morestable. In the invention, the ratio in solids concentration before andafter centrifugation is preferably 0.8 or higher, more preferably 0.9 orhigher, and particularly preferably 0.95 or higher.

In the self-dispersing resin, the content of water-soluble componentsthat exhibit water solubility when the self-dispersing resin is madeinto a dispersed state is preferably 10% by mass or less, morepreferably 8% by mass or less, and further more preferably 6% by mass orless. When the content of the water-soluble component is 10% by mass orless, swelling of polymer particles and fusion of polymer particles areeffectively suppressed, and relatively more stable dispersed state ismaintained; furthermore, an increase in the viscosity of the aqueous inkcomposition is prevented, and ejection stability is more favorable, forexample, in the case of employing the aqueous ink composition in aninkjet method.

The term “water-soluble component” as used herein refers to a compoundwhich is included in the self-dispersing resin, and which dissolves inwater when the self-dispersing resin is made into a dispersed state. Thewater-soluble component is a water-soluble compound which is generatedas a by-product or incorporated during the production of theself-dispersing resin.

The main chain of the water-insoluble resin is not particularly limited,and examples thereof include vinyl polymers and condensation polymers(such as epoxy resins, polyester, polyurethane, polyamide, cellulose,polyether, polyurea, polyimide, and polycarbonate). Vinyl polymers areparticularly preferable.

Preferable examples of the vinyl polymer and monomers for forming thevinyl polymer include those described in JP-A No. 2001-181549 and JP-ANo. 2002-88294. Another example of the vinyl polymer is a vinyl polymerhaving a dissociative group at a terminal of the polymer chain that hasbeen introduced by radical polymerization of a vinyl monomer using achain transfer agent, a polymerization initiator, or an iniferter, eachof which has a dissociative group (or a substituent that can bederivatized into a dissociative group), or by ion polymerization using acompound having a dissociative group (or a substituent that can bederivatized into a dissociative group) as either an initiator or aterminator.

Preferable examples of the condensation polymer and monomers for formingthe condensation polymer include those disclosed in JP-A No.2001-247787.

The particles of the self-dispersing resin preferably include awater-insoluble polymer that includes a hydrophilic structural unit anda structural unit derived from an aromatic-group-containing monomer or acyclic-aliphatic-group-containing monomer, from the viewpoint ofself-dispersibility.

The hydrophilic structural unit is not particularly limited as long asthe hydrophilic structural unit is derived from a monomer containing ahydrophilic group. The self-dispersing resin may include a structuralunit derived from only one type of hydrophilic-group-containing monomer,or may include structural units derived from two or more types ofhydrophilic-group-containing monomer. The hydrophilic group is notparticularly limited, and may be a dissociative group or a nonionichydrophilic group.

The hydrophilic group is preferably a dissociative group, and morepreferably an anionic dissociative group, from the viewpoints ofpromoting self-dispersion and the stability of the emulsified ordispersed state formed. Examples of the dissociative group include acarboxyl group, a phosphoric acid group, and a sulfonic acid group, anda carboxyl group is particularly preferable from the viewpoints offixing property of the ink composition obtained.

The hydrophilic-group-containing monomer is preferably a monomercontaining a dissociative group, and more preferably adissociative-group-containing monomer containing a dissociative groupand an ethylenic unsaturated bond, from the viewpoints ofself-dispersibility and aggregation properties. Thedissociative-group-containing monomer may be, for example, anunsaturated carboxylic acid monomer, an unsaturated sulfonic acidmonomer, or an unsaturated phosphoric acid monomer.

Examples of the unsaturated carboxylic acid monomer include acrylicacid, methacrylic acid, crotonic acid, itaconic acid, maleic acid,fumaric acid, citraconic acid, and 2-methacryloyloxymethylsuccinic acid.

Specific examples of the unsaturated sulfonic acid monomer includestyrenesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid,3-sulfopropyl (meth)acrylate, and a bis-(3-sulfopropyl)-itaconate ester.

Specific examples of unsaturated phosphoric acid monomer includevinylphosphonic acid, vinyl phosphate, bis(methacryloxyethyl)phosphate,diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethylphosphate, and dibutyl-2-acryloyloxyethyl phosphate.

Among the dissociative group-containing monomers, unsaturated carboxylicacid monomers are preferable from the viewpoints of dispersion stabilityand ejection stability, and acrylic monomers are more preferable, andacrylic acid and methacrylic acid are particularly preferable.

The particles of the self-dispersing resin preferably include a polymerhaving a carboxyl group, and more preferably include a polymer having acarboxyl group and an acid value of from 25 to 100 mgKOH/g, from theviewpoints of self-dispersibility and the aggregation speed whencontacting the treatment liquid during image formation using thetreatment liquid. The acid value is more preferably from 30 to 90mgKOH/g, and particularly preferably from 35 to 65 mgKOH/g, from theviewpoints of self-dispersibility and the aggregation speed whencontacting the treatment liquid. When the acid value is 25 mgKOH/g orhigher, the stability of self-dispersing properties is improved. Whenthe acid value is 100 mgKOH/g or lower, aggregation properties areimproved.

The aromatic-group-containing monomer is not particularly limited aslong as the monomer is a compound having an aromatic group and apolymerizable group. The aromatic group may be derived from an aromatichydrocarbon or derived from an aromatic heterocycle. In the invention,the aromatic group is preferably an aromatic group derived from anaromatic hydrocarbon from the viewpoint of particle shape stability inan aqueous medium.

The polymerizable group may be a condensation-polymerizable group or anaddition-polymerizable group. In the invention, from the viewpoint ofparticle shape stability in an aqueous medium, an addition-polymerizablegroup is preferable, and a group containing an ethylenically unsaturatedbond is more preferable.

The aromatic-group-containing monomer in the invention is preferably amonomer having an ethylenic unsaturated bond and an aromatic groupderived from an aromatic hydrocarbon. The aromatic-group-containingmonomer may be used singly, or in combination of two or more thereof.

Examples of the aromatic-group-containing monomer include phenoxyethyl(meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, andstyrene-containing monomers. Aromatic-group-containing (meth)acrylatemonomers are preferable, at least one selected from phenoxyethyl(meth)acrylate, benzyl (meth)acrylate, or phenyl (meth)acrylate is morepreferable, and phenoxyethyl (meth)acrylate, or benzyl (meth)acrylate isstill more preferable, from the viewpoints of thehydrophilicity/hydrophobicity balance of the polymer chain and inkfixability.

The term “(meth)acrylate” as used herein refers to acrylate ormethacrylate.

The cyclic-aliphatic-group-containing monomer is preferably a monomerhaving an ethylenic unsaturated bond and a cyclic aliphatic groupderived from a cyclic aliphatic hydrocarbon, and more preferably acyclic-aliphatic-group-containing (meth)acrylate monomer (hereinaftersometimes referred to as “alicyclic (meth)acrylate”).

The alicyclic (meth)acrylate refers to a compound which contains astructural moiety derived from (meth)acrylic acid and a structuralmoiety derived from an alcohol, in which the structural moiety derivedfrom an alcohol has a structure containing at least one substituted orunsubstituted alicyclic hydrocarbon group (i.e., cyclic aliphaticgroup). The alicyclic hydrocarbon group may be a structural moietyderived from an alcohol itself, or may be bound to the structural moietyderived from a hydroxyl group of an alcohol via a linking group.

The alicyclic hydrocarbon group may be, without particular limitation,any alicyclic hydrocarbon group that contains a cyclic non-aromatichydrocarbon group, and examples thereof include a monocyclic hydrocarbongroup, a bicyclic hydrocarbon group and a polycyclic hydrocarbon groupthat is tri- or higher-cyclic. Examples of the alicyclic hydrocarbongroup include: a cycloalkyl group such as a cyclopentyl group or acyclohexyl group; a cycloalkenyl group; a bicyclohexyl group; anorbornyl group; an isobornyl group; a dicyclopentanyl group; adicyclopentenyl group; an adamantyl group; a decahydronaphthalenylgroup; a perhydrofluorenyl group; a tricycle [5.2.1.0^(2,6)]decanylgroup; and bicyclo[4.3.0] nonane.

The alicyclic hydrocarbon group may itself have a substituent. Examplesof the substituent include an alkyl group, an alkenyl group, an arylgroup, an aralkyl group, an alkoxy group, a hydroxyl group, a primaryamino group, a secondary amino group, a tertiary amino group, analkylcarbonyl group, an arylcarbonyl group, and a cyano group. Thealicyclic hydrocarbon group may form a condensed ring. The alicyclichydrocarbon group used in the invention preferably has an alicyclichydrocarbon moiety having from 5 to 20 carbon atoms from the viewpointsof viscosity and solubility.

Specific examples of alicyclic (meth)acrylates are described below, butthe invention is not limited thereto.

Examples of alicyclic (meth)acrylates that are monocyclic includecycloalkyl (meth)acrylates containing a cycloalkyl group having from 3to 10 carbon atoms, such as cyclopropyl (meth)acrylate, cyclobutyl(meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate,cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, cyclononyl(meth)acrylate, and cyclodecyl (meth)acrylate.

Examples of alicyclic (meth)acrylates that are bicyclic includeisobornyl (meth)acrylate and norbornyl (meth)acrylate.

Examples of alicyclic (meth)acrylates that are tricyclic includeadamanthyl (meth)acrylate, dicyclopentanyl (meth)acrylate, anddicyclopentenyloxyethyl (meth)acrylate.

These alicyclic (meth)acrylates may be used singly, or in combination oftwo or more thereof.

From among the above, the alicyclic (meth)acrylate is preferably atleast one selected from a bicyclic (meth)acrylate or a polycyclic(meth)acrylate that is tri- or higher-cyclic, and more preferably atleast one of isobornyl (meth)acrylate, adamantyl (meth)acrylate, ordicyclopentanyl (meth)acrylate, from the viewpoints of the dispersionstability of the self-dispersing resin particles, fixability, andblocking resistance.

The self-dispersing resin is preferably an acrylic resin including astructural unit derived from a (meth)acrylate monomer, and morepreferably an acrylic resin including a structural unit derived from anaromatic-group-containing (meth)acrylate monomer or an alicyclic(meth)acrylate. The self-dispersing resin still more preferably includesa structural unit derived from an aromatic-group-containing(meth)acrylate monomer or an alicyclic (meth)acrylate, at a content offrom 10% by mass to 95% by mass with respect to the entire mass of theresin. When the content of the structural unit derived from anaromatic-group-containing (meth)acrylate monomer or an alicyclic(meth)acrylate is from 10% by mass to 95% by mass with respect to theentire mass of the resin, the stability of the self-emulsification orthe dispersed state is improved, and an increase in the ink viscositycan be further suppressed.

From the viewpoints of stability of self-dispersed state, stabilizationof a particle shape in an aqueous medium due to hydrophobic interactionbetween aromatic rings, and reduction in the amount of water-solublecomponents through hydrophobization of the particles to an appropriatedegree, the content of a structural unit derived from anaromatic-group-containing (meth)acrylate monomer or an alicyclic(meth)acrylate is more preferably from 15 to 90% by mass, further morepreferably from 15 to 80% by mass, and particularly preferably from 25to 70% by mass.

The self-dispersing resin may include a structural unit derived from anaromatic-group-containing monomer or a cyclic-aliphatic-group-containingmonomer (preferably, an alicyclic (meth)acrylate), and a structural unitderived from a dissociative-group-containing monomer. Theself-dispersing resin may further include at least one other structuralunit (additional structural unit), as necessary.

The monomer for forming the additional structural unit is notparticularly limited as long as the monomer is copolymerizable with thearomatic-group-containing monomer and the dissociative-group-containingmonomer. In particular, the monomer is preferably analkyl-group-containing monomer from the viewpoints of the flexibility ofthe polymer skeleton and the ease of the control of the glass transitiontemperature (Tg) of the polymer.

Examples of the alkyl-group-containing monomer include (meth)acrylatemonomers including alkyl (meth)acrylates such as methyl (meth)acrylate,ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate,n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate,hexyl (meth)acrylate, and ethylhexyl (meth)acrylate; ethylenicallyunsaturated monomers having a hydroxyl group, such as hydroxymethyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypentyl(meth)acrylate, and hydroxyhexyl (meth)acrylate; and dialkylamino alkyl(meth)acrylates such as dimethylaminoethyl (meth)acrylate; and(meth)acrylamide monomers including N-hydroxyalkyl (meth)acrylamidessuch as N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl(meth)acrylamide, and N-hydroxybutyl (meth)acrylamide; and N-alkoxyalkyl(meth)acrylamides such as N-methoxymethyl (meth)acrylamide,N-ethoxymethyl (meth)acrylamide, N-n-butoxymethyl(meth)acrylamide,N-isobutoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide,N-ethoxyethyl (meth)acrylamide, N-n-butoxyethyl (meth)acrylamide, andN-isobutoxyethyl (meth)acrylamide.

The molecular weight of the water-insoluble polymer that forms theself-dispersing resin particles, in terms of weight average molecularweight, is preferably from 3,000 to 200,000, and more preferably from5,000 to 150,000, and still more preferably from 10,000 to 100,000. Aweight average molecular weight of 3,000 or more effectively reduces theamount of water-soluble components. A weight average molecular weight of200,000 or less enhances the stability of self-dispersed state.

The weight average molecular weight is measured by gel permeationchromatography (GPC). Details of GPC are as described above.

The water-insoluble polymer that forms the self-dispersing resinparticles preferably includes a structural unit derived from anaromatic-group-containing (meth)acrylate monomer (preferably astructural unit derived from phenoxyethyl (meth)acrylate and/or astructural unit derived from benzyl (meth)acrylate) or a structural unitderived from a cyclic-aliphatic-group-containing monomer (preferably analicyclic (meth)acrylate), at a copolymerization ratio of from 15 to 80%by mass relative to the entire mass of the water-insoluble polymer, fromthe viewpoint of hydrophilicity/hydrophobicity control of the polymer.

From the viewpoint of controlling the hydrophobicity of the polymer, itis preferable that the water-insoluble polymer contains a structuralunit derived from an aromatic group-containing (meth)acrylate monomer oran alicyclic (meth)acrylate, at a copolymerization ratio of from 15 to80% by mass, a structural unit derived from a carboxyl group-containingmonomer, and a structural unit derived from an alkyl group-containingmonomer (preferably a structural unit derived from an alkyl ester of(meth)acrylic acid). It is more preferable that the water-insolublepolymer contains a structural unit derived from phenoxyethyl(meth)acrylate and/or a structural unit derived from benzyl(meth)acrylate, and/or a structural unit derived from isobornyl(meth)acrylate and/or a structural unit derived from adamanthyl(meth)acrylate and/or a structural unit derived from dicyclopentanyl(meth)acrylate, at a copolymerization ratio of from 15 to 80% by mass; astructural unit derived from a carboxyl group-containing monomer; and astructural unit derived from an alkyl group-containing monomer(preferably a structural unit derived from a C₁-C₄ alkyl ester of(meth)acrylic acid). Further, the water-insoluble polymer preferably hasan acid value of from 25 mgKOH/g to 100 mgKOH/g and a weight averagemolecular weight of from 3,000 to 200,000, and more preferably has anacid value of from 30 mgKOH/g to 90 mgKOH/g and a weight averagemolecular weight of from 5,000 to 150,000.

Specific examples of the water-insoluble resin for forming thewater-insoluble resin particles are described below. However, thewater-insoluble resin for forming the water-insoluble resin particles inthe invention is not limited thereto. The ratios in the parenthesesrepresent mass ratios between copolymerization components.

B-01: Phenoxyethyl acrylate/methyl methacrylate/acrylic acid copolymer(50/45/5)B-02: Phenoxyethyl acrylate/benzyl methacrylate/isobutylmethacrylate/methacrylic acid copolymer (30/35/29/6)B-03: Phenoxyethyl methacrylate/isobutyl methacrylate/methacrylic acidcopolymer (50/44/6)B-04: Phenoxyethyl acrylate/methyl methacrylate/ethyl acrylate/acrylicacid copolymer (30/55/10/5)B-05: Benzyl methacrylate/isobutyl methacrylate/methacrylic acidcopolymer (35/59/6)B-06: Styrene/phenoxyethyl acrylate/methyl methacrylate/acrylic acidcopolymer (10/50/35/5)B-07: Benzyl acrylate/methyl methacrylate/acrylic acid copolymer(55/40/5)B-08: Phenoxyethyl methacrylate/benzyl acrylate/methacrylic acidcopolymer (45/47/8)B-09: Styrene/Phenoxyethyl acrylate/butyl methacrylate/acrylic acidcopolymer (5/48/40/7)B-10: Benzyl methacrylate/isobutyl methacrylate/cyclohexylmethacrylate/methacrylic acid (35/30/30/5)B-11: Phenoxyethyl acrylate/methyl methacrylate/butylacrylate/methacrylic acid copolymer (12/50/30/8)B-12: Benzyl acrylate/isobutyl methacrylate/acrylic acid copolymer(93/2/5)B-13: Styrene/phenoxyethyl methacrylate/butyl acrylate/acrylic acidcopolymer (50/5/20/25)B-14: Styrene/butyl acrylate/acrylic acid copolymer (62/35/3)B-15: Methyl methacrylate/phenoxyethyl acrylate/acrylic acid copolymer(45/51/4)B-16: Methyl methacrylate/phenoxyethyl acrylate/acrylic acid copolymer(45/49/6)B-17: Methyl methacrylate/phenoxyethyl acrylate/acrylic acid copolymer(45/48/7)B-18: Methyl methacrylate/phenoxyethyl acrylate/acrylic acid copolymer(45/47/8)B-19: Methyl methacrylate/phenoxyethyl acrylate/acrylic acid copolymer(45/45/10)B-21: Methyl methacrylate/isobornyl methacrylate/methacrylic acidcopolymer (20/72/8, glass transition temperature: 180° C., I/O value:0.44)B-22: Methyl methacrylate/isobornyl methacrylate/methacrylic acidcopolymer (40/52/8, glass transition temperature: 160° C., I/O value:0.50)B-23: Methyl methacrylate/isobornyl methacrylate/dicyclopentanylmethacrylate/methacrylic acid copolymer (20/62/10/8, glass transitiontemperature: 170° C., I/O value: 0.44)B-24: Methyl methacrylate/dicyclopentanyl methacrylate/methacrylic acidcopolymer (20/72/8, glass transition temperature: 160° C., I/O value:0.47)

The particles of the water-insoluble resin are preferably particles of astyrene-acrylic resin, urethane resin, or a mixture thereof.

Examples of the styrene-acrylic resin include the acrylic resins whichcontains styrene as a copolymerization component, and which aredescribed above in the explanation of the self-dispersing resinparticles, and preferable embodiments thereof are also the same as inthe explanation of the self-dispersing resin particles. Specificexamples thereof include, but are not limited to, compounds B-06, B-09,B-13, and B-14 shown above.

The water-insoluble resin particles in the invention are preferably theurethane resin particles, from the viewpoint of improving continuousejection property and ejection stability of the ink composition. Sinceurethane resins are less vulnerable to deterioration by photolysis thanacrylic polymers, an image formed using an ink composition containing aurethane resin has excellent light fastness.

The urethane resin particle is preferably a particle containing at leastone urethane resin selected from the urethane resins represented by UP-1to UP-4 shown below.

In UP-1 to UP-4, R represents an aliphatic group or an aromatic group.R¹ represents —(CH₂)_(m)—COON or —(CH₂CH₂O)_(p)—CH₃; m represents aninteger of from 1 to 10,p represents an integer of from 1 to 100, Xrepresents NH or O, and n represents a positive integer.

Each of the urethane resins represented by UP-1 to UP-4 preferablyincludes a crosslink bond in the resin. The presence of a crosslink bondimproves the stability of the urethane resin particles against shearing.Each of the urethane resins represented by UP-1 to UP-4 preferablyincludes an acidic group from the viewpoint of improving the stabilityof the urethane resin particles.

Methods for producing the urethane resins represented by UP-1 to UP-4and preferable embodiments of the urethane resins are not particularlylimited, and a preferable exemplary method is the production methoddescribed in JP-A No. 2006-241457. Specifically, the production methoddescribed in JP-A No. 2006-141457 includes preparing an emulsioncontaining an isocyanate compound and an anionic surfactant, adding abifunctional, trifunctional, or polyfunctional reactive agent to theemulsion, and agitating the emulsion to generate a urethane resin.

From the viewpoint of aggregation speed, it is preferable that thewater-insoluble resin includes a polymer that has been synthesized in anorganic solvent, that the polymer has a carboxyl group, that some or allof the carboxyl groups of the polymer (which has an acid value ofpreferably from 25 to 100, more preferably from 30 to 90, and still morepreferably from 35 to 65) have been neutralized, and that the polymer isprepared in the form of a polymer dispersion of which the continuousphase is water. In other words, the preparation of the water-insolubleresin particles preferably includes a process of synthesizing a polymerin an organic solvent, and a dispersing process of forming an aqueousdispersion of the polymer of which some or all of the carboxyl groupsthereof have been neutralized.

The dispersing process preferably includes the following sub-processes(1) and (2).

Sub-process (1): a process of agitating a mixture containing the polymer(water-insoluble polymer), an organic solvent, a neutralizer, and anaqueous medium.Sub-process (2): a process of removing the organic solvent from themixture.

The sub-process (1) is preferably treatment in which the polymer(water-insoluble polymer) is dissolved in the organic solvent, and thenthe neutralizer and the aqueous medium are gradually added thereto, andmixed and agitated to form a dispersion. When a neutralizer and anaqueous medium are added to a water-insoluble polymer solution in whicha water-insoluble polymer is dissolved in an organic solvent as in theabove sub-process, self-dispersing resin particles of which the diameteris highly stable during storage can be obtained without requiring astrong shearing force. The method of agitating the mixture is notparticularly limited, and a generally-used mixing and agitationapparatus, and/or a disperser such as an ultrasonic disperser or ahigh-pressure homogenizer, may be used, as necessary.

Preferable examples of the organic solvent include alcohol solvents,ketone solvents, and ether solvents. Examples of alcohol solventsinclude isopropyl alcohol, n-butanol, t-butanol, and ethanol. Examplesof ketone solvents include acetone, methyl ethyl ketone, diethyl ketone,and methyl isobutyl ketone. Examples of ether solvents include dibutylether and dioxane. Among the above solvents, ketone solvents such asmethyl ethyl ketone and alcohol solvents such as isopropyl alcohol arepreferable. It is also preferable to use isopropyl alcohol and methylethyl ketone in combination, in order to make milder the polarity changefrom an oil phase to an aqueous phase at the time of phase inversion.Combined use of the solvents makes it possible to obtain self-dispersingresin particles having a very small particle diameter that are free fromaggregation precipitation or adhesion between the particles and thathave high dispersion stability. This is thought to be caused by milderpolarity change at the time of phase inversion from the oil phase to theaqueous phase.

The neutralizer is used to neutralize some or all of the dissociativegroups of the polymer so as to allow the polymer to get into a stableemulsion or dispersion state in water. When the water-insoluble resinparticles have anionic dissociative groups (such as carboxyl groups) asdissociative groups, the neutralizer to be used may be a basic compoundsuch as an organic amine compound, ammonia, or an alkali metalhydroxide. Examples of the organic amine compound includemonomethylamine, dimethylamine, trimethylamine, monoethylamine,diethylamine, triethylamine, monopropylamine, dipropylamine,monoethanolamine, diethanolamine, triethanolamine,N,N-dimethyl-ethanolamine, N,N-diethyl-ethanolamine,2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol,N-methyldiethanolamine, N-ethyldiethanolamine, monoisopropanolamine,diisopropanolamine, and triisopropanolamine. Examples of the alkalimetal hydroxide include lithium hydroxide, sodium hydroxide, andpotassium hydroxide. Among them, sodium hydroxide, potassium hydroxide,triethylamine, and triethanolamine are preferable from the viewpoint ofstabilization of the dispersion of the self-dispersing resin particlesaccording to the invention in water.

The amount of the basic compound to be used is preferably from 5 to 120%by mol, more preferably from 10 to 110% by mol, and still morepreferably from 15 to 100% by mol, with respect to 100% by mol of thedissociative group. When the amount of the basic compound is 5% by molor more, an effect of stabilizing the dispersion of the particles inwater can be exerted. When the amount of basic compound is 120% by molor less, an effect of reducing water-soluble components can be exerted.

In the sub-process (2), the organic solvent is removed from thedispersion obtained through the sub-process (1), by a common method suchas distillation under reduced pressure, whereby phase inversion into anaqueous system occurs and an aqueous dispersion of the self-dispersingresin particles is obtained. The organic solvent has substantially beenremoved from the obtained aqueous dispersion, and the amount of residualorganic solvent is preferably 0.2% by mass or less, and more preferably0.1% by mass or less.

The average particle diameter of the self-dispersing resin particles interms of volume average particle diameter is preferably in the range offrom 10 to 400 nm, more preferably from 10 to 200 nm, and still morepreferably from 10 nm to 100 nm. When the volume average particlediameter is 10 nm or more, suitability for production is improved. Whenthe average particle diameter is 400 nm or less, storage stability isimproved.

The particle size distribution of the self-dispersing resin particles isnot particularly limited, and may be wide or monodispersed. In anembodiment, a mixture of two or more types of water-insoluble particlesis used.

The average particle diameter and particle size distribution of theself-dispersing resin particles is obtained by measuring a volumeaverage particle diameter thereof by a dynamic light scattering methodusing a Nanotrac particle size distribution analyzer UPA-EX 150 (tradename, manufactured by Nikkiso Co., Ltd.).

The glass transition temperature (Tg) of the water-insoluble resinparticles is preferably 100° C. or higher, and more preferably 130° C.or higher, from the viewpoints of maintenance durability and ejectionproperty after maintenance. The upper limit of Tg is not particularlylimited, but is preferably 190° C.

In a preferable embodiment, the black ink composition includes thewater-insoluble resin particles in an amount larger than the totalamount (mass) of all coated pigments (including the mass of coatingresins, the same applies hereinafter) included in the ink composition.Since the amount of resin particles is large relative to the amount ofcoated pigments, and the relative amounts of the pigments, includingcarbon black, in the black ink composition (in the solids content of theblack ink composition) are reduced, an image with suppressedstreak-shaped unevenness is easily obtained, and generation of damage toa nozzle surface during maintenance is mitigated.

In particular, the ratio of the content of water-insoluble resinparticles relative to the total amount of coated pigments (i.e., amountof water-insoluble resin particles/total amount of coated pigments(including the amount of coating resins)) is preferably in the range offrom 1.0 to 5.0, and more preferably in the range of from 1.2 to 4.0.

The content of the water-insoluble resin particles in the black inkcomposition is preferably from 0.5 to 10% by mass, more preferably from1 to 9% by mass, and further more preferably from 3 to 9% by mass, withrespect to the total amount (mass) of the black ink composition. Whenthe content of water-insoluble resin particles is 0.5% by mass orhigher, the amounts of pigments are relatively low, whereby an image inwhich generation of streak-shaped unevenness is suppressed may easily beformed, and damage during maintenance is effectively suppressed. Acontent of water-insoluble resin particles of 10% by mass or less isadvantageous from the viewpoint of long-term ejection stability.

(Solid Humectant)

The black ink composition of the invention preferably further containsat least one solid humectant. The humectant refers to a water-solublecompound which is solid at 25° C. and has water retention ability.

Examples of the solid humectant include urea, urea derivatives,pyrrolidone derivatives, alkyl glycines or glycylbetaines represented byFormula 1 shown below, and sugars. The solid humectant may be usedsingly, or in combination of two or more thereof.

Examples of urea derivatives include compounds obtained by substitutinga hydrogen atom on at least one nitrogen atom of urea with at least onealkyl group or alkanol, thiourea, and compounds obtained by substitutingat least one hydrogen atom on at least one nitrogen atom of thioureawith at least one alkyl group or alkanol. Specific examples thereofinclude N-methylurea, N,N-dimethylurea, thiourea, ethylene urea,hydroxyethyl urea, hydroxybutyl urea, ethylene thiourea, and diethylthiourea.

Examples of pyrrolidone derivatives include compounds obtained bysubstituting the hydrogen atom on the nitrogen atom of pyrrolidone withan alkyl group or an alkanol. Specific examples thereof include2-methylpyrrolidone, N-methylpyrrolidone, N-octylpyrrolidone,N-laurylpyrrolidone, and β-hydroxyethylpyrrolidone.

Examples of alkyl glycines include compounds represented by Formula 1shown below. In Formula 1, R₁ and R₂ each independently represent alinear or branched alkyl group having from 1 to 5 carbon atoms, and Mrepresents a hydrogen atom, an alkali metal atom, or an alkaline earthmetal atom.

R₁R₂NCH₂COOM  Formula 1

Examples of alkyl glycines include N-methylglycine, N,N-dimethylglycine,N,N,N-trimethylglycine, N-ethyl-N-methylglycine, N,N-diethylglycine,N-isopropyl-N-methylglycine, N-isopropyl-N-ethylglycine,N,N-diisopropylglycine, N,N-dibutylglycine, N-butyl-N-methylglycine, andN-butyl-N-ethylglycine. Of these, N,N,N-trimethylglycine is preferablefrom the viewpoints of achieving less foaming of the ink, high ejectionstability, and excellent maintenance performance.

Examples of sugars include monosaccharides, disaccharides,oligosaccharides (including trisaccharides and tetrasaccharides), andpolysaccharides. Specific examples thereof include glucose, mannose,fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol(sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, andmaltotriose.

Herein, polysaccharides refer to sugars in a broad sense, and includevarious substances present in the nature, such as alginic acid,a-cyclodextrine, and cellulose.

Examples of derivatives of sugars include reducing sugars (such as sugaralcohols) and oxidized sugars (such as aldonic acid, uronic acid, aminoacid, or thiosugar) of the above-mentioned sugars. Sugar alcohols areparticularly preferably, and, among them, maltitol, sorbitol, andxylitol are preferable

Examples of sugar derivatives further include hyaluronic acid andhyaluronic acid salt, and a commercially-available sodium hyaluronate 1%aqueous solution (molecular weight=350,000) may be used as a hyarulonicacid salt.

Since the urea, the urea derivatives, the pyrrolidone derivatives, andthe sugars have high hydrogen bonding ability, these substances exertexcellent effects in terms of prevention of drying of an ink; furtheruse of these substances enable easy cleaning and removal even when anink containing particles of a highly hydrophobic polymer, such as awater-insoluble resin, is tightly adhered to a nozzle. The reasonthereof is not clear, it is presumed that a salt-forming group includedin the water-insoluble resin and the solid humectant interact with eachother through hydrogen bonding, as a result of which the tightly adheredink becomes easily re-dispersible. Furthermore, it is presumed that thehydrogen bonding interaction between a salt-forming group included inthe water-insoluble resin and the solid humectant contributes to theprevention of foaming of an ink.

Similarly, use of an alkyl glycine or glycylbetaine represented byFormula 1 enables easy cleaning and removal even when an ink containingparticles of a highly hydrophobic polymer, such as a water-insolubleresin in the invention, is tightly adhered onto a nozzle. It is presumedthat salting out occurs during the processes of drying and concentrationof an ink, which leads to aggregation of water-insoluble polymerparticles, as a result of which the water-insoluble polymer tightlyadheres onto a nozzle member. It is presumed that use of the alkylglycine or the glycylbetaine suppresses the tight adhesion of thewater-insoluble polymer onto a nozzle member, by interfering with theabove process.

From the viewpoints of a high moisture retention ability and easiness inremoval of ink residues, it is preferable to use at least one selectedfrom the group consisting of urea, a urea derivative, an alkyl glycineor glycylbetaine represented by Formula 1, maltitol, sorbitol, andxylitol, and it is more preferable to use at least one selected from thegroup consisting of urea and a urea derivative.

In particular, since urea and urea derivatives have high hydrotropicproperties, they work as an aid that improves the cleaning property(i.e., re-dispersibility) of a water-insoluble resin. Therefore, ureaand urea derivatives are preferably used.

The content of solid humectant in the black ink composition ispreferably from 5 to 30% by mass, more preferably from 5 to 20% by mass,and particularly preferably from 5 to 10% by mass, with respect to thetotal mass of the ink composition from the viewpoint of removability(cleaning property) of ink residues.

In the black ink composition, the ratio of the content of solidhumectant to the total amount of water-insoluble resin and all pigments(i.e., mass of solid humectant/total mass of water-insoluble resin andpigments) is preferably 0.01 or higher, more preferably in the range offrom 0.1 to 3.0, and most preferably in the range of from 0.5 to 2.0.

(Water)

The ink composition according to the invention may include water. Thecontent of water is not particularly limited, and is preferably from 10to 99% by mass, more preferably from 30 to 80% by mass, and still morepreferably from 50 to 70% by mass.

(Other Components)

In addition to the above components, the ink composition according tothe invention may further include other components, such as additives,as necessary. Examples of other components include known additives suchas anti-fading agents, emulsion stabilizers, penetration promoters,ultraviolet absorbers, preservatives, antifungal agents, pH adjusters,surface tension adjusters, defoaming agents, viscosity adjustmentagents, dispersants, dispersion stabilizers, antirust agents, andchelating agents. These various additives may be directly added afterthe preparation of the ink composition, or may be added during thepreparation of the ink composition. Specific examples of the additivesinclude the additives described as other additives in paragraphs [0153]to [0162] of JP-A No. 2007-100071.

Examples of surface tension adjusters include nonionic surfactants,cationic surfactants, anionic surfactants, and betaine surfactants. Thecontent of surface tension adjuster is preferably a content that adjuststhe surface tension of the ink composition to be from 20 to 60 mN/m,more preferably from 20 to 45 mN/m, and still more preferably from 25mN/m to 40 mN/m, in order to achieve favorable droplet ejection by aninkjet method. The surface tension of the ink composition can bemeasured at 25° C. using, for example, a plate method.

In regard to specific examples of surfactants, preferable hydrocarbonsurfactants include: anionic surfactants such as fatty acid salts, alkylsulfate ester salts, alkyl benzenesulfonates, alkylnaphthalenesulfonates, dialkyl sulfosuccinates, alkyl phosphate estersalts, naphthalenesulfonic acid-formalin condensates, andpolyoxyethylene alkyl sulfate ester salts; and nonionic surfactants suchas polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers,polyoxyethylene fatty acid esters, sorbitan fatty acid esters,polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines,glycerin fatty acid esters, and oxyethylene-oxypropylene blockcopolymers. Further, SURFYNOLS (trade name, manufactured by Air Productsand Chemicals, Inc.) and OLFINE E1010 (trade name, manufactured byNisshin Chemical Industry Co., Ltd.); which are acetylenepolyoxyethylene oxide surfactants, are preferably used. Moreover, amineoxide amphoteric surfactants such as N,N-dimethyl-N-alkylamine oxide arealso preferable. Further, surfactants described in pages 37 to 38 ofJP-A No. 59-157636, and Research Disclosure No. 308119 (1989) are alsousable. Use of fluorine (fluorinated alkyl) surfactants or siliconesurfactants, such as those described in JP-A Nos. 2003-322926,2004-325707, and 2004-309806, improves rubbing resistance.

The surface tension adjuster may be used as an antifoamer, and may be afluorine-containing compound, a silicone compound, or a chelate agent ofwhich a representative example is EDTA.

When an ink is applied by an inkjet method, from the viewpoint of inkdroplet ejection stability and coagulation speed, the viscosity of theblack ink composition according to the invention is preferably in therange of from 1 to 30 mPa·s, more preferably in the range of from 1 to20 mPa·s, still more preferably in the range of from 2 to 15 mPa·s, andparticularly preferably in the range of from 2 to 10 mPa·s. Theviscosity of the ink composition can be measured at 20° C. using, forexample, a Brookfield viscometer.

It is preferable that the black ink composition of the invention has apH of from 7.5 to 10 from the viewpoints of ink stability andaggregation speed. The pH is measured at 25° C. using a generally-usedpH analyzer.

In the image forming method according to the invention, image formationis preferably carried out using an ink set that includes the inkcomposition (and, optionally, ink compositions having other colors, asnecessary) and a treatment liquid capable of causing formation of anaggregate when contacting the ink composition. The ink set according tothe invention can be used in the form of an ink cartridge thatintegrally accommodates the ink composition(s) and treatment liquid(s)or ink cartridges that independently accommodate the ink composition(s)and treatment liquid(s). The use of the ink cartridge is preferable fromthe viewpoint of, for example, convenience in handling. Ink cartridgesconfigured to contain an ink set are known in the relevant technicalfield, and ink cartridge can be prepared by appropriately using knownmethods.

<Ink Set>

The ink set of the invention includes the black ink composition of theinvention, and a treatment liquid containing an aggregation componentcapable of causing formation of an aggregate when contacting thetreatment liquid. Since the ink set of the invention includes the blackink composition described above, a black image or an image ofintermediate tone (for example, gray) with less yellow tinge isobtained, the generation of streak-shaped unevenness and hue unevennessis suppressed, and the generation of damage to a head nozzle duringmaintenance is prevented even when he image is formed, for example, in asingle-pass manner at a high speed; as a result, a high-qualityachromatic image that does not exhibit a substantial color change for along period of time is obtained.

Details of the ink composition are as described above.

The treatment liquid used in the invention is an aqueous compositioncapable of causing formation of an aggregate when contacting the blackink composition. Specifically, the treatment liquid includes at least anaggregation component which , when mixed with the black ink composition,can aggregate dispersed particles such as coloring particles (such aspigment particles and water-insoluble resin particles) included in theblack ink composition, thereby forming an aggregate. The treatmentliquid may further include other components, if necessary. By using thetreatment liquid together with the ink composition, image formation byan inkjet method is carried out at a high speed, generation ofstreak-shaped unevenness or the like is suppressed, and an image with ahigh resolution is obtained even when high-speed image formation iscarried out.

The treatment liquid includes at least one aggregation component capableof forming an aggregate when contacting the ink composition. As a resultof the treatment liquid mixing with the ink composition ejected by aninkjet method, the aggregation of pigment and the like which have beenstably dispersed in the ink composition is promoted.

Examples of the treatment liquid include a liquid composition capable offorming an aggregate by changing the pH of the ink composition. Here,the pH)(25° C. of the treatment liquid is preferably from 1 to 6, morepreferably from 1.2 to 5, and still more preferably from 1.5 to 4, fromthe viewpoint of the coagulation speed of the ink composition. In thiscase, the pH (25° C.) of the ink composition used in the ink applicationprocess is preferably from 7.5 to 9.5 (more preferably from 8.0 to 9.0).

In particular, it is preferable that the ink composition has a pH of 7.5or more at 25° C., and that the treatment liquid has a pH of from 3 to 5at 25° C., from the viewpoints of improvement of image density andresolution, and achievement of high-speed inkjet recording.

The aggregation component may be used singly, or in combination of twoor more thereof.

The treatment liquid may be configured to include at least one acidiccompound as an aggregation component. Examples of the acidic compoundinclude a compound having a phosphoric acid group, a phosphonic acidgroup, a phosphinic acid group, a sulfuric acid group, a sulfonic acidgroup, a sulfinic acid group, or a carboxyl group, or a salt thereof(for example, a polyvalent metal salt). Among them, a compound having aphosphoric acid group or a carboxyl group is preferable, and a compoundhaving a carboxyl group is more preferable, from the viewpoint of thecoagulation speed of the ink composition.

The compound having a carboxyl group is preferably selected frompolyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid,maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid,citric acid, tartaric acid, lactic acid, pyrrolidone carboxylic acid,pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid,pyridine carboxylic acid, coumalic acid, thiophene carboxylic acid,nicotinic acid, or a derivative of any of these compounds or a salt(such as a polyvalent metal salt) of any of these compounds. Thesecompounds may be used singly, or in combination of two or more thereof.

The treatment liquid in the invention may further include an aqueoussolvent (such as water) in addition to the acidic compound.

The content of acidic compound in the treatment liquid is preferablyfrom 5 to 95% by mass, and more preferably from 10 to 80% by mass, withrespect to the total mass of the treatment liquid from the viewpoint ofaggregation effect.

A preferable example of the treatment liquid that improves high-speedcoagulation properties may be a treatment liquid that contains apolyvalent metal salt or polyallylamine. Examples of the polyvalentmetal salt include salts of alkali earth metals (such as magnesium andcalcium) belonging to Group 2 of the Periodic Table, salts of transitionmetals (such as lanthanum) belonging to Group 3 of the Periodic Table,salts of metals (such as aluminum) of Group 13 of the Periodic Table,and salts of lanthanides (such as neodymium). Further examples ofaggregation components include polyallylamine and polyallylaminederivatives. Carboxylic acid salts (such as formic acid salts, aceticacid salts, and benzoic acid salts), nitric acid salts, chloride salts,and thiocyanic acid salts are suitable as metal salts. In particular, acalcium or magnesium salt of a carboxylic acid (such as formic acid,acetic acid, or benzoic acid), a calcium or magnesium salt of nitricacid, calcium chloride, magnesium chloride, and a calcium or magnesiumsalt of thiocyanic acid, are preferable.

The content of metal salt in the treatment liquid is preferably from 1to 10% by mass, more preferably from 1.5 to 7% by mass, and still morepreferably from 2 to 6% by mass, with respect to the entire mass of thetreatment liquid.

The viscosity of the treatment liquid is preferably in the range of from1 to 30 mPa·s, more preferably in the range of from 1 to 20 mPa·s, stillmore preferably from 2 to 15 mPa·s, and particularly preferably from 2to 10 mPa·s, from the viewpoint of the coagulation speed of the inkcomposition. The viscosity is measured under a condition of 20° C. usinga VISCOMETER TV-22 (trade name, manufactured by TOKI SANGYO CO., LTD).

The treatment liquid has a surface tension of preferably from 20 to 60mN/m, more preferably from 20 to 45 mN/m, and further more preferablyfrom 25 to 45 mN/m, from the viewpoint of aggregation speed of the inkcomposition. The surface tension is measured using an automatic surfacetensiometer CBVP-Z (trade name, manufactured by Kyowa Interface ScienceCo., Ltd.) at 25° C.

<Image Forming Method>

The image forming method according to the invention includes: an inkapplication process of applying the above-described black inkcomposition according to the invention onto a recording medium by aninkjet method; and a treatment liquid application process of applying,onto the recording medium, a treatment liquid containing an aggregationcomponent capable of causing formation of an aggregate when contactingthe black ink composition. The image forming method according to theinvention may further include other processes, such as a heating fixingprocess of fixing, by heating, the ink image formed by the applicationof the ink composition onto the recording medium, as necessary.

Since the black ink composition described above is used, an achromaticimage with a high quality and less yellow tinge, and in which generationof streak-shaped unevenness is suppressed is obtained for a long periodof time, while damage to a head nozzle surface during maintenance issuppressed.

—Treatment Liquid Application Process—

In the treatment liquid application process, a treatment liquidcontaining an aggregation component capable of causing formation of anaggregate when contacting the ink composition is applied onto arecording medium. The specifics of the treatment liquid used in thepresent process, such as the components of the treatment liquid andpreferable embodiments thereof, are as described above.

The application of the treatment liquid can be performed employing aknown method such as a coating method, an inkjet method, or a dippingmethod. The coating method may be a known coating method using, forexample, a bar coater, an extrusion die coater, an air doctor coater, ablade coater, a rod coater, a knife coater, a squeeze coater, or areverse roll coater. The specifics of the inkjet method are the same asin the ink application process described below.

The treatment liquid application process may be conducted either beforeor after the ink application process described below. In the invention,an embodiment in which the ink application process is conducted afterthe treatment liquid application process is preferable. That is, anembodiment in which the treatment liquid for aggregating a colorant(preferably, a pigment) in the ink composition is applied onto arecording medium in advance of the application of the ink composition,and then the ink composition is applied so as to contact the treatmentliquid that has been applied onto the recording medium, thereby formingan image, is preferable. This embodiment allows image formation to becarried out at higher speeds, and an image having high density and highresolution can be obtained even when high-speed recording is performed.

The amount of the treatment liquid to be applied is not particularlylimited as long as the treatment liquid is capable of coagulating theink composition. The amount of the treatment liquid to be applied ispreferably an amount such that the amount of aggregation componentsapplied is 0.1 g/m² or larger. In particular, the amount of thetreatment liquid to be applied is more preferably an amount such thatthe amount of aggregation components applied is from 0.1 to 1.0 g/m²,and more preferably from 0.2 to 0.8 g/m². When the amount of aggregationcomponents applied is 0.1 g/m² or more, the aggregation reactionproceeds favorably. When the amount of aggregation components applied is1.0 g/m² or less, gloss is not excessively high, and thus the amount ispreferable.

In the invention, it is preferable that the ink application process isconducted after the treatment liquid application process, and that aheating and drying process of drying the treatment liquid on therecording medium by heating is further conducted during a period fromafter the application of the treatment liquid onto the recording mediumto the application of the ink composition. Drying of the treatmentliquid by heating performed in advance of the ink application processrealizes favorable ink spotting properties such as bleed prevention, andrealizes recording of a visible image having excellent color density andexcellent hue.

The drying by heating may be conducted by using a known heating meanssuch as a heater, a blowing means utilizing air blow such as a dryer, ora combination thereof. The heating may be performed according to, forexample, a method of applying heat, by using a heater or the like, froma side of the recording medium opposite to the face applied with thetreatment liquid, a method of blowing warm or hot air to the face of therecording medium applied with the treatment liquid, or a method ofheating by using an infrared heater. Alternatively, two or more of thesemethods may be combined and used for the heating.

—Ink Application Process—

In the ink application process, the above-described ink composition isapplied onto a recording medium by an inkjet method, to form a blackimage. The specifics of the ink composition used in the present process,such as the specifics of the components and preferable embodiments, areas described above.

The inkjet method is not particularly limited, and may be any knownmethod such as a charge-control method in which ink is ejected byelectrostatic attraction force, a piezo-inkjet method in which ink isejected using a piezoelectric device that generates a mechanicaldeformation when a voltage is applied, an acoustic inkjet method inwhich ink is ejected using a radiation pressure generated by irradiationof ink with acoustic beams that have been converted from electricsignals, and a thermal inkjet method in which ink is ejected using apressure generated by formation of bubbles caused by heating of ink(BUBBLEJET, registered trademark).

Specific methods of the inkjet method include a method in which a largenumber of small-volume droplets of an ink having a low concentration,which is referred to as a photoink, are ejected, a method in whichplural inks having different concentrations and substantially the samehue are used so as to improve the image quality, and a method in which acolorless and clear ink is used.

A piezoelectric inkjet method is suitable for use as the inkjet methodin the invention. The combination of the black ink composition of theinvention or the ink set including the black ink composition with thepiezoelectric inkjet method improves the continuous ejection propertyand ejection stability of an ink.

In the piezoelectric inkjet method, the distortion mode of apiezoelectric element may be any one of a bending mode, a longitudinalmode, or a sheer mode. The configuration of the piezoelectric elementand the structure of the piezo head are not particularly limited, andany one of known techniques may be used.

The ink nozzles and other members used for recording by an inkjet methodare not particularly limited, and may be selected, as appropriate, inaccordance with the purpose.

The inkjet method to be employed may be a shuttle system in whichrecording is carried out while a short serial head is moved in the widthdirection of a recording medium, or a line system in which a line headat which recording elements are arranged so as to correspond to theentire length of one side of the recording medium. In the line system,an image can be recorded on the entire surface of a recording medium bysimply moving the recording medium in the direction perpendicular to thedirection in which the recording elements are arranged. In addition,since only the recording medium is moved, recording at a recording speedhigher than that in the shuttle system can be achieved.

The liquid droplet volume of the ink ejected from the inkjet head ispreferably from 0.2 to 10 pl (pico-liter), and more preferably from 0.4to 5 pl. The Maximum total ejection amount of ink during image recordingis preferably in the range of from 10 to 36 ml/m², and more preferablyin the range of from 15 to 30 ml/m².

—Heating and Fixing Process—

In the invention, it is preferable that a heating and fixing process offixing the ink composition on the recording medium by heating is carriedout after the ink application process. In the heating and fixingprocess, the recorded image formed by the application of the treatmentliquid and the ink composition is fixed to the recording medium byheating. By conducting the heating and fixing treatment, the image isfixed onto the recording medium, and the rubbing resistance of the imagecan be further improved. Therefore, the image forming method accordingto the invention preferably includes the heating and fixing process.

The heating is preferably carried out at a temperature that is equal toor higher than the minimum film-forming temperature (MFT) of thewater-insoluble resin particles in the image. Heating to the MFT orhigher transforms the particles into a film, thereby strengthening theimage.

When pressure is applied together with heat, the pressure to be appliedis preferably from 0.1 to 3.0 MPa, more preferably from 0.1 to 1.0 MPa,and further more preferably from 0.1 to 0.5 MPa, from the viewpoint ofsurface smoothing.

The method of heating is not particularly limited, and preferableexamples thereof include a noncontact drying method, such as a method ofheating with a heat generator such as a NICHROME wire heater, a methodof supplying warm or hot air, or a method of heating with a halogenlamp, an infrared lamp, or the like. The method of applying heat andpressure is not particularly limited, and preferable examples thereofinclude a contact heating and fixing method, such as a method ofpressing a hot plate against an image-formed surface of the recordingmedium, a method in which a heat-pressurization apparatus is used topass the recording medium through a pressure contact portion, whereinthe heat-pressurization apparatus may have a pair of heat-pressurizationrollers or a pair of heat-pressurization belts, or may have aheat-pressurization belt disposed at the image-recorded surface side ofthe recording medium and a support roller disposed at the opposite sideof the recording medium. The pressure contact portion is thus formedbetween the pair of rollers or between the pair of heat-pressurizationbelts or between the heat-pressurization belt and the support roller.

When heat and pressure are applied, the nip time is preferably from 1msec to 10 sec, more preferably from 2 msec to 1 sec, and still morepreferably from 4 msec to 100 msec. The nip width is preferably from 0.1mm to 100 mm, more preferably from 0.5 mm to 50 mm, and still morepreferably from 1 mm to 10 mm.

The heat-pressurization roller may be a metal roller made of metal, or aroller having a metal core of which the outer surface is covered with acoating layer made of an elastic material and, optionally, a surfacelayer (also referred to as a release layer). The metal core in thelatter case may be, for example, a cylindrical body made of iron,aluminum, or SUS (stainless steel). It is preferable that at least apart of the surface of the metal core is coated with a coating layer.The coating layer is preferably formed by a silicone resin orfluororesin, each of which has release properties. It is preferable thata heat generator is placed in the interior of the metal core of one ofthe heat-pressurization rollers. Heating treatment and pressureapplication treatment may be performed simultaneously by passing therecording medium between the rollers. In an embodiment, the recordingmedium is heated by being nipped between two heating rollers, ifnecessary. Preferable examples of the heat generator include a halogenlamp heater, a ceramic heater, and a NICHROME wire.

The belt substrate for forming the heat-pressurization belt for use inthe heat-pressurization apparatus is preferably a seamless electroformednickel, and the thickness of the substrate is preferably from 10 μm to100 μm. Examples of the material of the belt substrate include aluminum,iron, and polyethylene, as well as nickel. When a silicone resin layeror a fluororesin layer is provided, the thickness of the layer formed bythe resin is preferably from 1 μm to 50 μm, and more preferably from 10μm to 30 μm.

In order to obtain pressure (nip pressure) within the above range,elastic members that exhibit tension, such as a spring, may be selectedand disposed at both ends of a roller (for example, aheat-pressurization roller), such that a desired nip pressure can beobtained in consideration of the nip gap.

When the heat-pressurization rollers or heat-pressurization belts areused, the conveyance speed of the recording medium is preferably from200 mm/sec to 700 mm/sec, more preferably from 300 mm/sec to 650 mm/sec,and still more preferably from 400 mm/sec to 600 mm/sec.

—Recording Medium—

In the image forming method according to the invention, the recordingmedium on which an image is to be formed is not particularly limited,and may be coated paper used for general offset printing and the like,or paper specialized for inkjet recording.

The coated paper is paper obtained by applying a coating material onto asurface of high-quality paper or acid-free paper, which iscellulose-based and generally not surface-treated, to form a coatinglayer. The coated paper may be a commercially available product.Specific examples thereof include high-quality papers (A) such as PRINCEWOOD FREE (trade name) manufactured by Oji Paper Co., Ltd., SHIRAOI(trade name) manufactured by Nippon Paper Industries Co., Ltd., and NewNPI jo-shitsu (New NPI high-quality; trade name) manufactured by NipponPaper Industries Co., Ltd.; Bitokoshi (very light weight coated papers)such as EVER LIGHT COATED (trade name) manufactured by Oji Paper Co.,Ltd. and AURORA S (trade name) manufactured by Nippon Paper IndustriesCo., Ltd.; lightweight coat papers (A3) such as TOPKOTE (L) (trade name)manufactured by Oji Paper Co., Ltd. and AURORA L (trade name)manufactured by Nippon Paper Industries Co., Ltd.; coat papers (A2, B2)such as TOPKOTE PLUS (trade name) manufactured by Oji Paper Co., Ltd.and AURORA COAT (trade name) manufactured by Nippon Paper IndustriesCo., Ltd.; and art papers (A1) such as 2/SIDE GOLDEN CASK GLOSS (tradename) manufactured by Oji Paper Co., Ltd. and TOKUBISHI ART (trade name)manufactured by Mitsubishi Paper Mills Ltd.

The coated paper is a material which absorbs ink only slowly. However,in the invention, even when such a material is used, an image in whichgeneration of image transfer between recording media is suppressed andwhich has excellent rubbing resistance, is recorded at a high speed.Therefore, use of a coated paper is preferable.

EXAMPLES

Hereinafter, the present invention will be specifically described withreference to Examples, but the present invention is not limited to theseExamples, and encompasses any other embodiments that do not depart fromthe spirit of the invention: Unless stated otherwise, “part(s)”represents part(s) by mass.

Synthesis Example Synthesis of Water-Insoluble Polymer 1

88 g of methyl ethyl ketone was added to a 1000 mL three-necked flaskequipped with a stirrer and a condenser tube, and was heated to 72° C.under a nitrogen atmosphere. To this, a solution obtained by dissolving0.86 g of dimethyl-2,2′-azobisisobutyrate, 60 g of benzyl methacrylate,10 g of methacrylic acid, and 30 g of methyl methacrylate in 50 g ofmethyl ethyl ketone was added dropwise over 3 hours. After the additionwas completed, the mixture was reacted for one more hour, and then asolution obtained by dissolving 0.40 g ofdimethyl-2,2′-azobisisobutyrate in 2 g of methyl ethyl ketone was addedthereto. The temperature was raised to 80° C., and the mixture washeated for 4 hours. The resulting reaction liquid was reprecipitatedtwice in an excess amount of hexane, and the separated resin was driedto obtain 96 g of a water-insoluble polymer 1.

The composition of the polymer obtained was confirmed by ¹H-NMR, and theweight average molecular weight (Mw) thereof as determined by GPC was43,300. The acid value of the polymer was measured by the methodaccording to JIS K0070 (1992), and was found to be 64.6 mgKOH/g.

(Preparation of Resin-Coated Carbon Black Dispersion A)

The components in the formulation described below were mixed, and theresulting mixture was subjected to dispersion for a period of from 3hours to 6 hours using a bead mill with zirconia beads having a diameterof 0.1 mm. Subsequently, from the resulting dispersion, the methyl ethylketone was removed under reduced pressure at 55° C., and, further, aportion of water was removed, to prepare a resin-coated carbon blackdispersion A having a carbon black concentration of 15.0% by mass.

<Formulation of Resin-Coated Carbon Black Dispersion A>

Carbon black (NIPEX180-IQ, trade name, manufactured 10.0 parts byEvonik-Degussa GmbH) Water-insoluble polymer 1 (water-insoluble resin) 5.5 parts Methyl ethyl ketone (organic solvent) 30.5 parts 1 mol/l NaOHaqueous solution (neutralizer agent)  7.7 parts Ion-exchange water 96.3parts

(Preparation of Carbon Black Dispersion B)

5 parts of a styrene-acrylic acid copolymer (JONCRYL 678 (trade name)manufactured by BASF Japan Ltd., having a molecular weight of 8,500 andan acid value of 215 mgKOH/g) as a water-soluble dispersant, 2.0 partsof dimethylaminoethanol, and 78.0 parts of ion exchanged water weremixed by stirring at 70° C. to obtain a solution. Subsequently, to thissolution, 15 parts of carbon black (NIPEX 180-IQ (trade name)manufactured by Evonik Degussa Japan Co., Ltd.) were added and premixed.Thereafter, the resulting mixture was dispersed using a sand grinderfilled with 0.5 mm zirconia beads at a volume ratio of 50%, to prepare acarbon black dispersion B having a carbon black content of 15% by mass.

(Preparation of Resin-Coated Cyan Pigment Dispersion A)

Preparation of a Resin-Coated Cyan Pigment Dispersion a was Conducted inthe Same manner as the preparation of resin-coated carbon blackdispersion A, except that the formulation used in the preparation of theresin-coated carbon black dispersion A was changed to the followingformulation. As a result, a resin-coated cyan pigment dispersion Ahaving a cyan pigment concentration of 15% by mass was obtained.

<Formulation of Resin-Coated Cyan Pigment Dispersion A>

PB 15/3 pigment powder (phthalocyanine blue A220, trade 10.0 parts name,manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.)Water-insoluble polymer 1 (water-insoluble resin)  4.0 parts Methylethyl ketone (organic solvent) 30.5 parts 1 mol/l NaOH aqueous solution(neutralizer agent)  5.6 parts Ion-exchange water 98.7 parts

(Preparation of Cyan Pigment Dispersion B)

Preparation of a Cyan Pigment Dispersion B was Conducted in the SameManner as the preparation of the carbon black dispersion B, except thatthe carbon black in the preparation of the carbon black dispersion B waschanged to PB 15:3 pigment powder (PHTHALOCYANINE BLUE A220 (trade name)manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.). As aresult, a cyan pigment dispersion B having a cyan pigment content of 15%by mass was obtained.

(Preparation of Resin-Coated Magenta Pigment Dispersion A)

Preparation of a Resin-Coated Magenta Pigment Dispersion a was Conductedin the same manner as the preparation of the resin-coated cyan pigmentdispersion A, except that the formulation used in the preparation of theresin-coated cyan pigment dispersion A was changed to the followingformulation. As a result, a resin-coated magenta pigment dispersion Ahaving a magenta pigment concentration of 15% by mass was obtained.

<Formulation of Resin-Coated Magenta Pigment Dispersion A>

PR122 pigment powder (CROMOPHTAL JET MAGENTA 10.0 parts DMQ, trade name,manufactured by BASFJapanLtd.) Water-insoluble polymer 1(water-insoluble resin)  3.0 parts Methyl ethyl ketone (organic solvent)30.5 parts 1 mol/l NaOH aqueous solution (neutralizer agent)  4.2 partsIon-exchange water 102.3 parts 

(Preparation of Magenta Pigment Dispersion B)

Preparation of a Magenta Pigment Dispersion B was Conducted in the SameManner as the preparation of the cyan pigment dispersion B, except thatthe PB 15:3 pigment powder used in the preparation of the cyan pigmentdispersion B was changed to PR 122 pigment powder (trade name:CROMOPHTAL JET MAGENTA DMQ, manufactured by BASF Japan Ltd.). As aresult, a magenta pigment dispersion B having a magenta pigment contentof 15% by mass was obtained.

(Preparation of Resin-Coated Yellow Pigment Dispersion A)

Preparation of a Resin-Coated Yellow Pigment Dispersion a was Conductedin the Same manner as the preparation of the resin-coated cyan pigmentdispersion A, except that the formulation used in the preparation of theresin-coated cyan pigment dispersion A was changed to the followingformulation. As a result, a resin-coated yellow pigment dispersion Ahaving a yellow pigment concentration of 15% by mass was obtained.

<Formulation of Resin-Coated Yellow Pigment Dispersion A>

PY74 pigment powder (trade name: HANSA BRILLIANT 10.0 parts YELLOW5GX03, manufactured by Clariant) Water-insoluble polymer 1(water-insoluble resin)  4.3 parts Methyl ethyl ketone (organic solvent)30.5 parts 1 mol/l NaOH aqueous solution (neutralizer agent)  6.0 partsIon-exchange water 99.2 parts

(Preparation of Yellow Pigment Dispersion B)

Preparation of a Yellow Pigment Dispersion B was Conducted in the SameManner as the preparation of the resin-coated cyan pigment dispersion B,except that the PB 15:3 pigment powder used in the preparation of theresin-coated cyan pigment dispersion B was changed to PY74 pigmentpowder (tradename: HANSA BRILLIANT YELLOW 5GX03, manufactured byClariant). As a result, a resin-coated yellow pigment dispersion Bhaving a yellow pigment concentration of 15% by mass was obtained.

(Preparation of Aqueous Dispersion of Self-Dispersing Polymer C-1)

First, 540.0 g of methyl ethyl ketone was put into a 2 L-three neckedflask equipped with a mechanical stirrer, a thermometer, a refluxcondenser, and a nitrogen gas-introducing pipe, and was heated to 75° C.While the temperature in the reaction vessel was maintained at 75° C., amixed solution of 108 g of methyl methacrylate, 388.8 g of isobornylmethacrylate, 43.2 g of methacrylic acid, 108 g of methyl ethyl ketone,and 2.16 g of V-601 (trade name, manufactured by Wako Pure ChemicalIndustries Ltd.) was added dropwise at a constant speed such that thedropwise addition was completed in 2 hours. After completion of theaddition, a solution containing 1.08 g or V-601 and 15.0 g of methylethyl ketone was added thereto, followed by stirring at 75° C. for 2hours. Thereafter, a solution containing 0.54 g or V-601 and 15.0 g ofmethyl ethyl ketone was further added thereto, followed by stirring at75° C. for 2 hours. The reaction solution was heated to 85° C. andstirred for 2 hours, thereby obtaining a resin solution containing amethyl methacrylate/isobornyl methacrylate/methacrylic acid copolymer(=20/72/8 [mass ratio]).

The copolymer obtained had a weight average molecular weight (Mw) of61,000 and an acid value of 52.1 mgKOH/g. The weight average molecularweight was measured by gel permeation chromatography (GPC), and isexpressed in terms of a polystyrene-equivalent value. In GPC, HLC-8020GC(trade name, manufactured by Tosoh Corporation) was used, and TSKgelSuper HZM-H, TSKgel Super HZ4000, and TSKgel Super HZ200 (trade names,manufactured by Tosoh Corporation) were used as columns, andtetrahydrofuran (THF) was used as an eluting solvent. The acid value wasmeasured in accordance with the method of JIS K0700 (1992).

Subsequently, 588.2 g of the resin solution was weighed out, 165 g ofisopropanol and 120.8 ml of an aqueous 1 mol/L sodium hydroxide solutionwere added thereto, and the temperature in the reaction vessel wasincreased to 80° C. Next, 718 g of distilled water was added dropwise ata speed of 20 ml/min to form a water dispersion. Thereafter, solvent wasdistilled off by maintaining the temperature in the reaction vessel at80° C. for 2 hours, at 85° C. for 2 hours, and at 90° C. for 2 hoursunder atmospheric pressure. Then, the pressure in the reaction vesselwas reduced to distill off isopropanol, methyl ethyl ketone, anddistilled water, thereby obtaining an aqueous dispersion of aself-dispersing polymer C-1 (resin particles) having a solids content of26.0% by mass.

—Preparation of Aqueous Dispersions of Self-dispersing Polymers C-2 andC-3—

An aqueous dispersion of a self-dispersing polymer C-2 and an aqueousdispersion of a self-dispersing polymer C-3 were prepared in the samemanner as the preparation of the aqueous dispersion of theself-dispersing polymer C-1, except that the kinds and ratios ofmonomers used in the preparation of the aqueous dispersion of theself-dispersing polymer C-1 were changed as described below.

Self-dispersing polymer C-2: methyl methacrylate/dicyclopentanylmethacrylate/methoxy polyethylene glycol methacrylate (n=2)/methacrylicacid copolymer (=54/35/5/6 [mass ratio])

The copolymer obtained as a result of the preparation had a weightaverage molecular weight (Mw) of 60,000 and an acid value of 39.1mgKOH/g. The solids content of the aqueous dispersion was 25% by mass.

Self-dispersing polymer C-3: n-butyl methacrylate/cyclohexylmethacrylate/styrene/acrylic acid copolymer (=30/55/10/5 [mass ratio])

The copolymer obtained as a result of the preparation had a weightaverage molecular weight (Mw) of 58,000 and an acid value of 38.9mgKOH/g. The solids content of the aqueous dispersion was 25% by mass.

Actually measured values of glass transition temperatures of theself-dispersing polymers C-1 to C-3 (measured Tg) are shown in Table 1below. The measured Tg was obtained by the following method.

<Measured Tg>

First, an amount of the aqueous dispersion of resin particlescorresponding to a solids amount of 0.5 g was dried under a reducedpressure at 50° C. for 4 hours, thereby obtaining a polymer solid. Thepolymer solid obtained was used as a sample for measurement of Tg usinga differential scanning calorimeter (DSC) EXSTAR 6220 (trade name,manufactured by SII Nano Technology Inc.). The measurement was carriedout as follows: 5 mg of the sample was put in an aluminum pan, thealuminum pan was tightly sealed, and the sample was subjected totemperature changes under a nitrogen atmosphere according to thetemperature profile described below. Then, a temperature correspondingto the peak top of DDSC in the second temperature increase in theobserved data was used as a measured Tg.

30° C.→−50° C. (cooling at 50° C./min)

−50° C.→120° C. (heating at 20° C./min)

120° C.→−50° C. (cooling at 50° C./min)

−50° C.→120° C. (heating at 20° C./min)

TABLE 1 Aqueous Dispersion of Self-dispersing Polymer Tg [° C.] C-1 180C-2 100 C-3 86

The thus-obtained aqueous dispersions of the self-dispersing polymerswere used for preparing inks having the formulations shown in Table 2,and the inks were subjected to filtration using a membrane filter (φ=0.2μm), thereby producing Inks A to V. The addition amounts of respectivecomponents shown in Table 2 are amounts (mass %) relative to the totalamount of the ink.

TABLE 2 Ink A Ink B Ink C Ink D Ink E Invention Invention InventionInvention Invention Carbon black dispersion A 10.0 8.0 6.7 13.3 13.3(dispersed using water-insoluble polymer) CAB-O-JE300 (self-dispersingcarbon black) Carbon black dispersion B (dispersed using water-insolublepolymer) Cyan pigment dispersion A 3.3 2.8 2.3 3.3 2.8 (dispersed usingwater-insoluble polymer) Cyan pigment dispersion B (dispersed usingwater-insoluble polymer) Magenta pigment dispersion A 4.6 3.7 2.8 4.63.1 (dispersed using water-insoluble polymer) Magenta pigment dispersionB (dispersed using water-insoluble polymer) Yellow pigment dispersion A(dispersed using water-insoluble polymer) Yellow pigment dispersion B(dispersed using water-insoluble polymer) SANNIX GP250 8.0 8.0 8.0 8.08.0 (NEWPOL GP250, Sanyo Chemical Industries) Tripropylene glycolmonomethyl ether 3.0 3.0 3.0 3.0 3.0 Dipropylene glycol 5.0 5.0 5.0 5.05.0 OLFIN E1010 1.0 1.0 1.0 1.0 1.0 JONCRYL 586 (water-soluble) Aqueousdispersion of self-dispersing 28.0 32.0 32.0 24.0 polymer C-1(water-insoluble polymer; Tg = 180° C.) Aqueous dispersion ofself-dispersing 20.0 polymer C-2 (water-insoluble polymer; Tg = 100° C.)Aqueous dispersion of self-dispersing polymer C-3 (water-insolublepolymer; Tg = 86° C.) Urea 5.0 5.0 5.0 5.0 5.0 Carnauba wax 6.7 6.7 6.76.7 6.7 Ion-exchange water 25.4 24.8 27.6 30.1 28.1 Total 100.0 100.0100.0 100.0 100.0 Ink F Ink G Ink H Ink I Ink J Invention InventionInvention Invention Invention Carbon black dispersion A 10.0 10.0 8.06.7 8.7 (dispersed using water-insoluble polymer) CAB-O-JE300(self-dispersing carbon black) Carbon black dispersion B (dispersedusing water-insoluble polymer) Cyan pigment dispersion A 2.7 2.0 3.9 3.33.5 (dispersed using water-insoluble polymer) Cyan pigment dispersion B(dispersed using water-insoluble polymer) Magenta pigment dispersion A2.7 2.7 6.1 1.7 4.8 (dispersed using water-insoluble polymer) Magentapigment dispersion B (dispersed using water-insoluble polymer) Yellowpigment dispersion A 1.0 (dispersed using water-insoluble polymer)Yellow pigment dispersion B (dispersed using water-insoluble polymer)SANNIX GP250 8.0 8.0 8.0 8.0 8.0 (NEWPOL GP250, Sanyo ChemicalIndustries) Tripropylene glycol monomethyl ether 3.0 3.0 3.0 3.0 3.0Dipropylene glycol 5.0 5.0 5.0 5.0 5.0 OLFIN E1010 1.0 1.0 1.0 1.0 1.0JONCRYL 586 (water-soluble) Aqueous dispersion of self-dispersing 32.032.0 32.0 32.0 polymer C-1 (water-insoluble polymer; Tg = 180° C.)Aqueous dispersion of self-dispersing 32.0 polymer C-2 (water-insolublepolymer; Tg = 100° C.) Aqueous dispersion of self-dispersing polymer C-3(water-insoluble polymer; Tg = 86° C.) Urea 5.0 5.0 5.0 5.0 5.0 Carnaubawax 6.7 6.7 6.7 6.7 6.7 Ion-exchange water 24.0 24.7 21.4 27.7 21.3Total 100.0 100.0 100.0 100.0 100.0 Ink K Ink L Ink M Ink N InventionComparative Comparative Comparative Carbon black dispersion A 13.3 13.35.3 15.3 (dispersed using water-insoluble polymer) CAB-O-JE300(self-dispersing carbon black) Carbon black dispersion B (dispersedusing water-insoluble polymer) Cyan pigment dispersion A 3.3 2.7 3.7(dispersed using water-insoluble polymer) Cyan pigment dispersion B(dispersed using water-insoluble polymer) Magenta pigment dispersion A4.6 3.3 4.9 (dispersed using water-insoluble polymer) Magenta pigmentdispersion B (dispersed using water-insoluble polymer) Yellow pigmentdispersion A (dispersed using water-insoluble polymer) Yellow pigmentdispersion B (dispersed using water-insoluble polymer) SANNIX GP250 8.08.0 8.0 8.0 (NEWPOL GP250, Sanyo Chemical Industries) Tripropyleneglycol monomethyl ether 3.0 3.0 3.0 3.0 Dipropylene glycol 5.0 5.0 5.05.0 OLFIN E1010 1.0 1.0 1.0 1.0 JONCRYL 586 (water-soluble) Aqueousdispersion of self-dispersing 34.0 polymer C-1 (water-insoluble polymer;Tg = 180° C.) Aqueous dispersion of self-dispersing 32.0 polymer C-2(water-insoluble polymer; Tg = 100° C.) Aqueous dispersion ofself-dispersing 32.0 32.0 polymer C-3 (water-insoluble polymer; Tg = 86°C.) Urea 5.0 5.0 5.0 5.0 Carnauba wax 6.7 6.7 6.7 6.7 Ion-exchange water18.1 26.0 26.0 15.5 Total 100.0 100.0 100.0 100.0 Ink O Ink P Ink QComparative Comparative Comparative Carbon black dispersion A 5.3 16.76.7 (dispersed using water-insoluble polymer) CAB-O-JE300(self-dispersing carbon black) Carbon black dispersion B (dispersedusing water-insoluble polymer) Cyan pigment dispersion A 3.3 1.3 1.7(dispersed using water-insoluble polymer) Cyan pigment dispersion B(dispersed using water-insoluble polymer) Magenta pigment dispersion A4.0 1.7 2.5 (dispersed using water-insoluble polymer) Magenta pigmentdispersion B (dispersed using water-insoluble polymer) Yellow pigmentdispersion A (dispersed using water-insoluble polymer) Yellow pigmentdispersion B (dispersed using water-insoluble polymer) SANNIX GP250 8.08.0 8.0 (NEWPOL GP250, Sanyo Chemical Industries) Tripropylene glycolmonomethyl ether 3.0 3.0 3.0 Dipropylene glycol 5.0 5.0 5.0 OLFIN E10101.0 1.0 1.0 JONCRYL 586 (water-soluble) Aqueous dispersion ofself-dispersing polymer C-1 32.0 32.0 32.0 (water-insoluble polymer; Tg= 180° C.) Aqueous dispersion of self-dispersing polymer C-2(water-insoluble polymer; Tg = 100° C.) Aqueous dispersion ofself-dispersing polymer C-3 (water-insoluble polymer; Tg = 86° C.) Urea5.0 5.0 5.0 Carnauba wax 6.7 6.7 6.7 Ion-exchange water 24.7 17.7 26.5Total 100.0 100.0 100.0 Ink R Ink S Ink T Comparative ComparativeComparative Carbon black dispersion A 13.3 (dispersed usingwater-insoluble polymer) CAB-O-JE300 10.0 (self-dispersing carbon black)Carbon black dispersion B 10.0 (dispersed using water-insoluble polymer)Cyan pigment dispersion A 4.7 3.3 (dispersed using water-insolublepolymer) Cyan pigment dispersion B 3.3 (dispersed using water-insolublepolymer) Magenta pigment dispersion A 6.0 4.6 (dispersed usingwater-insoluble polymer) Magenta pigment dispersion B 4.6 (dispersedusing water-insoluble polymer) Yellow pigment dispersion A (dispersedusing water-insoluble polymer) Yellow pigment dispersion B (dispersedusing water-insoluble polymer) SANNIX GP250 8.0 8.0 8.0 (NEWPOL GP250,Sanyo Chemical Industries) Tripropylene glycol monomethyl ether 3.0 3.03.0 Dipropylene glycol 5.0 5.0 5.0 OLFIN E1010 1.0 1.0 1.0 JONCRYL 586(water-soluble) Aqueous dispersion of self-dispersing polymer C-1 32.032.0 32.0 (water-insoluble polymer; Tg = 180° C.) Aqueous dispersion ofself-dispersing polymer C-2 (water-insoluble polymer; Tg = 100° C.)Aqueous dispersion of self-dispersing polymer C-3 (water-insolublepolymer; Tg = 86° C.) Urea 5.0 5.0 5.0 Carnauba wax 6.7 6.7 6.7Ion-exchange water 13.3 21.4 21.4 Total 100.0 100.0 100.0 Ink U Ink VComparative Comparative Carbon black dispersion A 10.0 10.0 (dispersedusing water-insoluble polymer) CAB-O-JE300 (self-dispersing carbonblack) Carbon black dispersion B (dispersed using water-insolublepolymer) Cyan pigment dispersion A 3.3 3.3 (dispersed usingwater-insoluble polymer) Cyan pigment dispersion B (dispersed usingwater-insoluble polymer) Magenta pigment dispersion A 4.6 4.6 (dispersedusing water-insoluble polymer) Magenta pigment dispersion B (dispersedusing water-insoluble polymer) Yellow pigment dispersion A (dispersedusing water-insoluble polymer) Yellow pigment dispersion B (dispersedusing water-insoluble polymer) SANNIX GP250 8.0 8.0 (NEWPOL GP250, SanyoChemical Industries) Tripropylene glycol monomethyl ether 3.0 3.0Dipropylene glycol 5.0 5.0 OLFIN E1010 1.0 1.0 JONCRYL 586(water-soluble) 16.7 Aqueous dispersion of self-dispersing polymer C-1(water-insoluble polymer; Tg = 180° C.) Aqueous dispersion ofself-dispersing polymer C-2 (water-insoluble polymer; Tg = 100° C.)Aqueous dispersion of self-dispersing polymer C-3 (water-insolublepolymer; Tg = 86° C.) Urea 5.0 5.0 Carnauba wax 6.7 6.7 Ion-exchangewater 53.4 36.7 Total 100.0 100.0

Details of the components shown in Table 2 are as described below.

CAB-O-JET300: self-dispersing carbon black (solids concentration: 15% bymass, manufactured by Cabot Corporation)

OLFIN E1010: nonionic surfactant, manufactured by Nissin ChemicalIndustry Co., Ltd.

JONCRYL 586: water-soluble polymer (solids concentration: 30% by mass,manufactured by Johnson Polymer)

Carnauba wax: CELLOSOL 524, manufactured by Chukyo Yushi Co., Ltd.

(Preparation of Treatment Liquid)

Ingredients were mixed to form the following formulation, therebypreparing a treatment liquid. In regard to the physical properties ofthe treatment liquid, the treatment liquid had a viscosity of 2.6 mPa·s,a surface tension of 37.3 mN/m, and a pH of 1.6. The surface tension wasmeasured using an automatic surface tensiometer CBVP-Z (trade name,manufactured by Kyowa Interface Science Co., Ltd.) at 25° C. Theviscosity was measured using a viscometer TV-22 (trade name,manufactured by Toki Sangyo Co., Ltd.) at 20° C. The pH was measured at25° C.

<Formulation>

Malonic acid (manufactured by Wako Pure 15.0% by mass ChemicalIndustries Co., Ltd.) Diethylene glycol monomethyl ether (manufacturedby 20.0% by mass Wako Pure Chemical Industries Co., Ltd.) SodiumN-oleyl-N-methyl taurine  1.0% by mass Ion-exchange water 64.0% by mass

<Image Recording and Evaluation>

—1. Image Recording—

A printer for evaluation equipped with a print head GELJET GX5000 (tradename, manufactured by Ricoh Co., Ltd., full-line head) was prepared, andstorage tanks connected to the print head were filled with the inks A toN, respectively. Further, “TOKUBISHI ART DOUBLE-SIDED N” (trade name,manufactured by Mitsubishi Paper Mills, Ltd.: water absorptioncoefficient Ka=0.21 mL/m²·ms^(1/2)) as a recording medium was prepared.

Subsequently, the TOKUBISHI ART DOUBLE-SIDED N was fixed on a stage thatwas movable at 500 mm/sec in a predetermined linear direction that wouldbecome a vertical scanning direction at the time of recording. Then, thetreatment liquid was applied thereto using a wire bar coater in anamount of 2.0 g/m², and dried at 50° C. for 2 seconds immediately afterdrying. Next, a GELJET GX500 printer head was positioned such that thedirection of the line head was inclined at an angle of 75.7° withrespect to the direction (horizontal scanning direction) perpendicularto the movement direction (vertical scanning direction) of the stage onthe same plane. While the recording medium was moved in the verticalscanning direction at a constant speed, a solid image was printed in aline printing manner under the conditions of and ink droplet amount of2.8 pL, an ejection frequency of 24 kHz, a resolution of 1200 dpi×1200dpi, and a moving speed of the stage of 50 mm/s. Immediately afterprinting, the ink was dried at 60° C. for 3 seconds, and the recordingmedium was passed between a pair of fixation rollers heated at 60° C. soas to conduct fixation treatment at a nip pressure of 0.25 MPa with anip width of 4 mm, as a result of which an image sample was obtained.

Next, image samples were produced under the conditions in which themoving speed of the stage was changed from 50 mm/s to 100 mm/s or 250mm/s, and the ejection frequency was changed so as to maintain the samedroplet amount as that described above.

The fixation rollers were configured by a heating roller composed of ametal cylinder which is made of stainless steel (SUS), and which has ahalogen lump therein, and a silicone resin that covers the surface ofthe metal cylinder, and a counter roller that is in pressure contactwith the heating roller.

—2. Evaluation—

(1) Maintenance Durability Test

The inks shown in Table 2 were used in the test. Each ink was ejectedfrom a head nozzle until the amount of the ink that had been ejectedbecame an ink amount corresponding to continuously image printing on1,000 sheets. Thereafter, a cleaning liquid was applied to the surfaceof the head nozzle, and ink stains as well as the cleaning liquid wereremoved off using a wiping cloth (TORAYSEE MK cloth, trade name,manufactured by Toray Industries Inc.) After this operation was repeated3,000 times, the head surface was observed under a microscope, andevaluated in accordance with the following evaluation criteria.

<Evaluation Criteria>

A: Almost no scratch was observed.B: Scratches were slightly observed, but the extent of scratches waspractically tolerable.C: Scratches were observed, and the extent of scratches was practicallyintolerableD: Scratches were remarkable.

(2) Ejection Property Test

The ejection property test described below was performed before andafter the maintenance durability test using the inks shown in Table 2.

In the ejection property test, a line image of 75×24,000 dpi was printedat an ejection frequency of 12 kHz. In the image recording, “KASSAISHASHIN-SHIAGE Pro” (trade name, manufactured by Fuji Film Corporation)was used as a recording medium, application of the treatment liquid andthe subsequent drying were not carried out, and the recorded medium wasnot passed between the fixation rollers. Next, the central value of thelines was measured using a dot analyzer DA-6000 (trade name,manufactured by Oji Scientific Instruments), a standard deviation a ofthe positional deviation of each line was calculated, and the ejectionproperty was evaluated in accordance with the following evaluationcriteria.

<Evaluation Criteria>

A: σ was less than 2 μm, which indicates an excellent ejection property.B: σ was from 2 μm to less than 5 μm, which indicates a practicallytolerable ejection property.C: σ was from 5 μm to less than 7 μm, which indicates a practicallyintolerable ejection property.D: σ was 7 μm or more.

(3) Streak-shaped Unevenness in Image

100% solid images of 1200 dpi×1200 dpi were formed using the inks shownin Table 2, and were visually evaluated in accordance with the followingevaluation criteria.

<Evaluation Criteria>

A: Almost no streak-shaped unevenness was observed in the image.B: Slight streak-shaped unevenness was observed in the image, and thedegree of the unevenness was practically tolerable.C: Streak-shaped unevenness was observed in the image, and the degree ofthe unevenness was practically intolerable.D: Streak-shaped unevenness was remarkable.

(4) Color Deviation of Image

First, solid gray images having a resolution of 1200 dpi×1200 dpi andhaving densities ranging from 10% to 100% at an increment of 10% wereformed using each of the inks shown in Table 2, and L*a*b* values (L*₁,a*₁, b*₁) of each gray image was measured using a SPECTRO EYE (tradename, manufactured by X-rite). L*a*b* values (L*₂, a*₂, b*₂) in anon-image region (recording medium) was also measured. Based on themeasured values, the color difference (ΔEab) between the gray image andthe non-image region was calculated, and was evaluated in accordancewith the following evaluation criteria. The (ΔEab) was calculatedaccording to the following expression.

ΔEab={(a* ₁ −a* ₂)²+(b* ₁ −b* ₂)²}^(1/2)

<Evaluation Criteria>

A: ΔEab was smaller than 3, which indicates little color deviation, andfavorable result with respect to suppression of color deviation.B: ΔEab was in a range of from 3 to 4, which indicates practicallytolerable color deviation.C: ΔEab was in a range of from 5 to 7, which indicates practicallyintolerable color deviation.D: ΔEab was larger than 7, which indicates significantly large colordeviation.

(5) Image Density

100% solid images of 1200 dpi×1200 dpi were formed using the inks shownin Table 2. The image density (Dv: Visual Density) of each image wasmeasured using a SPECTRO EYE (trade name, manufactured by X-rite), andevaluated in accordance with the following evaluation criteria.

<Evaluation Criteria>

A: Dv was larger than 1.8, which indicates a favorable result withrespect to image density.B: Dv was in a range from 1.5 to 1.8, which indicates a practicallytolerable result with respect to image density.C: Dv was smaller than 1.5, which indicates a practically intolerableresult with respect to image density.

TABLE 3 Content ratio of Total amount of Total amount of Water-insolubleWater-insoluble resin/total Ink carbon black (*1) pigments (*2) coatedpigments (*3) resin (*4) amount of coated pigments Remarks A 1.5% 2.7%3.9% 7.0% 1.78 Invention B 1.2% 2.2% 3.2% 8.0% 2.52 Invention C 1.0%1.8% 2.6% 8.0% 3.11 Invention D 2.0% 3.2% 4.7% 5.0% 1.06 Invention E2.0% 2.9% 4.3% 6.0% 1.40 Invention F 1.5% 2.3% 3.4% 8.0% 2.35 InventionG 1.5% 2.2% 3.3% 8.0% 2.45 Invention H 1.2% 2.7% 3.9% 8.0% 2.08Invention I 1.0% 1.8% 2.6% 8.0% 3.11 Invention J 1.3% 2.7% 3.9% 8.0%2.05 Invention K 2.0% 3.2% 4.7% 8.0% 1.70 Invention L 2.0% 2.0% 3.1%8.0% 2.58 Comparative M 0.8% 1.7% 2.5% 8.5% 3.47 Comparative N 2.3% 3.6%5.3% 8.0% 1.51 Comparative O 0.8% 1.9% 2.7% 8.0% 2.94 Comparative P 2.5%3.0% 4.5% 8.0% 1.79 Comparative Q 1.0% 1.6% 2.4% 8.0% 3.36 Comparative R2.0% 3.6% 5.3% 8.0% 1.52 Comparative S 1.5% 2.7% 1.6% 8.0% 5.01Comparative T 1.5% 2.7% — 8.0% — Comparative U 1.5% 2.7% 3.9% — —Comparative V 1.5% 2.7% 3.9% — — Comparative (*1): Content ratio ofcarbon black (excluding coating resin) relative to the total amount ofink [mass %] (*2): Ratio of pigments (excluding coating resins) relativeto the total amount of ink [mass %] (*3): Ratio of coated pigments(including coating resins) relative to the total amount of ink [mass %](*4): Ratio of water-insoluble resin (excluding coating resins) relativeto the total amount of ink [mass %]

TABLE 4 Ejection property Maintenance Before After Streak-shaped ColorInk durability maintenance maintenance unevenness deviation Imagedensity Remarks A A A A A A A Invention B A A A A A A Invention C A A AA A B Invention D A A A A A A Invention E A A B A B A Invention F A A AA B A Invention G A A A A B A Invention H A A A A B A Invention I A A AA B B Invention J A A A A A A Invention K A A B A A A Invention L C A CB D A Comparative M A A A A C C Comparative N C A C C C A Comparative OA A A A D C Comparative P C A C C D A Comparative Q A A A B C CComparative R B A B B B A Comparative S B A B C B A Comparative T C A CC B A Comparative U C B D D B A Comparative V C C D D B A Comparative

As shown in Table 4, according to the invention, gray images withsuppressed little yellow tinge were obtained, the generation ofstreak-shaped unevenness in the formed images was suppressed, andexcellent image quality was achieved. Furthermore, the generation ofscratches which otherwise tends to be generated on a head surface duringa wiping operation for maintenance was prevented.

In contrast, in Comparative Examples, the gray images had yellow tinge,and streak-shaped unevenness was generated in images, which indicatethat the image quality was significantly inferior as compared to theExamples according to the invention. Furthermore, scratches wereobserved on a head surface after maintenance, which indicates lowdurability when the black ink is used.

1. A black ink composition, comprising: carbon black and a firstwater-insoluble resin that covers at least a part of a surface of thecarbon black; a cyan pigment and a second water-insoluble resin thatcovers at least a part of a surface the cyan pigment; a magenta pigmentand a third water-insoluble resin that covers at least a part of asurface of the magenta pigment; water-insoluble resin particles; andwater, wherein a content ratio of the carbon black is from 1.0 to 2.0%by mass with respect to a total mass of the composition, and a totalamount of pigments is from 1.8 to 3.5% by mass with respect to the totalmass of the composition.
 2. The black ink composition according to claim1, wherein a content of the water-insoluble resin particles is largerthan a total amount of pigments, at least a part of surfaces of whichare coated with water-insoluble resins, and the water-insoluble resinsthat cover the at least a part of surfaces of the pigments.
 3. The blackink composition according to claim 2, wherein a ratio of the content ofthe water-insoluble resin particles to the total amount of pigments, atleast a part of surfaces of which are coated with water-insolubleresins, and the water-insoluble resins that cover the at least a part ofsurfaces of the pigments, is more than 1.0 but not more than 4.0.
 4. Theblack ink composition according to claim 1, wherein the water-insolubleresin particles comprise self-dispersing polymer particles.
 5. The blackink composition according to claim 1, wherein the water-insoluble resinparticles have a Tg of 100° C. or higher.
 6. The black ink compositionaccording to claim 1, further comprising a solid humectant.
 7. The blackink composition according to claim 6, wherein the humectant is selectedfrom urea, a urea derivative, or a mixture thereof.
 8. The black inkcomposition according to claim 1, further comprising a yellow pigmentand a fourth water-insoluble resin that covers at least a part of asurface of the yellow pigment.
 9. An ink set, comprising: the black inkcomposition according to claim 1; and a treatment liquid comprising anaggregation component which is capable of causing formation of anaggregate when contacting the black ink composition.
 10. An imageforming method, comprising: applying the black ink composition accordingto claim 1 to a recording medium by an inkjet method; and applying atreatment liquid to the recording medium, the treatment liquidcomprising an aggregation component which is capable of causingformation of an aggregate when contacting the black ink composition. 11.The image forming method according to claim 10, wherein the applying ofthe black ink composition comprises applying the black ink compositionby a piezoelectric inkjet method.
 12. The image forming method accordingto claim 11, further comprising heating an image formed through theapplying of the black ink composition and the applying of the treatmentliquid, to fix the image on the recording medium.